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Ozone stress and antioxidant substances in Trifolium repens and Centaurea jacea leaves.

Ozone-sensitive (NC-S clone) and resistant plants (NC-R clone) of Trifolium repens and Centaurea jacea were exposed to moderate ozone concentrations in ambient air. The aim of this study was the investigation of the relation between ozone-sensitivity and leaf concentrations of antioxidants (ascorbic acid, total phenolics and total antioxidant capacity). NC-R clone showed the highest concentrations of antioxidants with 50-70% more ascorbic acid than NC-S. NC-R had about 5 times more ascorbic acid in the young leaves and 9 times more in the old leaves than Centaurea. In a fumigation experiment with acute ozone stress (100 nl L(-1)) the antioxidant levels changed profoundly. The ozone-injured leaves of NC-S had 6-8 times more total phenolics than uninjured leaves. Generally older leaves had lower antioxidant concentrations and were more prone to ozone injury than younger leaves. Ascorbic acid concentrations were closer related to the appearance of visible ozone injury than the other antioxidative parameters.

Antioxidants↗

Ozone, area social conditions, and mortality in Mexico City.

We investigated whether the association of daily mortality and ambient ozone differs by age and area social conditions of the region of residence using a time-series analysis. The study setting was metropolitan Mexico City, a high altitude city situated in a valley, with an estimated 20 million inhabitants, large socioeconomic gradients, and ozone levels frequently exceeding international standards. We stratified daily deaths by six census-derived socioeconomic indicators, based on characteristics of the county where decedents lived. We used Poisson regression to model the association between daily mortality and ozone levels (on the day of death and the previous day) in separate models, stratified by area socioeconomic level and age, and controlling for time trends and temperature. Ozone was positively associated with total mortality [0.65% increase per 10 ppb increment, 95% confidence interval (CI): 0.02%, 1.28%] and for mortality among those over age 65 [1.39% increase per 10 ppb increment, 95% CI: 0.51%, 2.28%]. Associations between ozone and all-age mortality did not show any consistent patterns according to socioeconomic gradients. We conclude that elderly people are at higher risk for ozone-associated mortality. Though county-level social indicators in Mexico City were not strong markers of vulnerability to ozone-associated acute mortality in this analysis, complex associations between individual and area-level factors may exist that would require additional data and further analyses to elucidate.

Age Factors↗

Degradation of trichothecene mycotoxins by aqueous ozone.

The degradation of ten trichothecene mycotoxins by aqueous ozone was monitored by liquid chromatography-ultraviolet-mass spectrometry (LC-UV-MS). Saturated aqueous ozone ( approximately 25 ppm) degraded these mycotoxins to materials that were not detected by UV or MS. At lower levels (approximately 0.25 ppm) of aqueous ozone, intermediate products were observed. On the basis of UV and MS data, it is proposed that the degradation begins with attack of ozone at the C9-10 double bond with the net addition of two atoms of oxygen. The remainder of the molecule appears to have been left unaltered. The oxidation state at the allylic carbon 8 position had a significant effect on the ease of reaction, as determined by moles of ozone required to effect oxidation. The amount of ozone required to effect oxidation to intermediate products and subsequent degradation followed the series allylic methylene (no oxygen) < hydroxyl (or ester) < keto. Ozonation was also sensitive to pH. At pH 4-6, all mycotoxins studied degraded readily; at pH 7-8 the degree of reactivity was dependent upon the carbon 8 oxidation state; at pH 9, there was little or no reaction. Structures for some of the intermediate products are proposed.

Chromatography, Liquid↗

Vitamin supplementation does not protect against symptoms in ozone-responsive subjects.

Vitamin supplements have been reported to reduce the magnitude of symptoms in subjects exposed to oxidant air pollution. To confirm whether supplementation with vitamins C and E could reduce lung function decrements, airway inflammation, and epithelial injury in subjects sensitive to ozone, a double-blinded, crossover control study was performed. Fourteen ozone-responsive subjects were randomly exposed to both air and ozone (0.2 ppm for 2 h) after 7 days of either placebo treatment or supplementation with vitamin C (500 mg/day) and E (100 mg/day). Lung function was assessed pre- and immediately postexposure and blood samples were taken at set intervals. Inflammatory, tissue injury, and antioxidant responses were examined in lavage fluid obtained by bronchoscopy 6 h postexposure. Exposure to ozone resulted in significant (P < 0.01) decrements in FEV1 with no protection observed following vitamin supplementation (-8.5%) versus placebo (-7.3%) treatment. Similarly, ozone-induced neutrophilia were of a similar magnitude after both treatments (P < 0.05). This lack of protection was observed despite elevated plasma vitamin C (+60.1%) and vitamin E (+51.4%) concentrations following supplementation, and increased vitamin C concentrations in the airways after supplementation following ozone exposure. These data do not therefore support the contention that acute ozone-induced symptoms can be attenuated through the use of dietary antioxidants in well-nourished individuals.

Air Pollutants↗

A realistic evaluation of the action of ozone on whole human blood.

We have clarified the role of the ozone concentration in relation to the resistance of human erythrocytes in whole human blood or in blood diluted either in saline or in distilled water. Spectrophotometric data related to haemoglobin were evaluated by exposing samples of fresh human blood directly to ozone doses (ratio 1:1 volume), within the therapeutic range (0.21-1.68 mM) and to one toxic dose (3.36 mM). Furthermore, the same determinations have been carried out after previous dilution of the same blood with either pure water or physiological saline (1 ml blood + 29 ml diluent) followed by ozonation with the above reported ozone doses. Addition of either saline or water implies a dilution of plasma antioxidants and also total haemolysis after water dilution. Particularly the latter case represents a most unphysiological situation because the osmotic shock causes the solubilization of the erythrocytic content. While it is possible to demonstrate that after haemolysis there is an ozone-concentration dependent transformation of some oxyhaemoglobin to methaemoglobin, no such process occurs after ozonation of whole blood. The results of this study fully confirm our previous data that judicious ozone doses neither damage erythrocytes, nor induce oxidation of intracellular haemoglobin. We hope that our conclusions will definitively clarify the absence of toxicity of ozonetherapy.

Blood↗

Laboratory-scale application of fiber optic transflection dip probe (FOTDP) for in situ monitoring of gas phase ozone in unsaturated porous media.

A fiber optic transflection dip probe (FOTDP) system was developed for in situ and real-time monitoring of the transport of gas phase ozone in unsaturated porous media. A unique property of this system is the employment of a dip probe, which is inserted within the porous media. At the probe's tip, incoming light interacts with gas phase ozone and is partially reflected back into the probe by a mirror attached to the tip. Calibration of the FOTDP system was successfully carried out with various ozone concentrations using a column packed with glass beads. The ozone breakthrough curves (BTCs) were obtained by converting normalized UV intensities into gas phase ozone concentrations. The FOTDP system worked well for in situ monitoring of gas phase ozone using a column packed with sand under various water saturations in the presence of SOM and reflected the ideal transport phenomena of gas phase ozone for various flow rates.

Animals↗

Decomposition of 2-naphthalenesulfonate in electroplating solution by ozonation with UV radiation.

This study investigates the ozonation of 2-naphthalenesulfonate (2-NS) combined with UV radiation in the electroplating solution. 2-NS is commonly used as a brightening and stabilization agent in the electroplating solution. Semibatch ozonation experiments were conducted under various reaction conditions to study the effects of ozone dosage and UV radiation on the oxidation of 2-NS. The concentrations of 2-NS were analyzed at specified time intervals to elucidate the decomposition of 2-NS. Total organic carbon (TOC) is chosen as a mineralization index of the ozonation of 2-NS. In addition, values of pH and oxidation reduction potential were continuously measured in the course of experiments. As a result, the nearly complete mineralization of 2-NS via the ozonation treatment can be achieved. The mineralization of 2-NS is found accelerated by the introduction of UV radiation and has a distinct relationship with the consumption of applied ozone. These results can provide useful information for the proper removal of 2-NS in the electroplating solution by the ozonation with UV radiation.

Electroplating↗

Degradation of 17alpha-ethinylestradiol in aqueous solution by ozonation.

This study investigates the ozonation of 17alpha-ethinylestradiol (EE(2)) in aqueous solution. The affecting factors on the degradation of EE(2) were studied and described in details, such as initial EE(2) concentration, initial pH value and ozone concentration. In addition, some parameters such as pH, electrical conductivity, mineralization efficiency and degradation products were monitored during the process. The mineralization efficiency of EE(2) could reach 53.9%. During the ozonation process the rapid decrease of pH and the sharp increase of electrical conductivity indicated the formation of acidic by-products, small fragments and ions which were confirmed by high performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GC/MS) analysis. Results showed that there were intermediate products of smaller molecule with higher polarity produced during the course of EE(2) degradation. Then a possible reaction pathway for EE(2) degradation involving all intermediates detected is proposed. During the ozonation process EE(2) was first oxidized into hydroxyl-semiquinone isomers which were subsequently degraded into low molecular weight compounds such as oxalic acid, malonate, glutarate, and so on. Furthermore, these organic acids are easily oxidized by ozone into carbon dioxide (CO(2)). This work shows that ozonation process is promising for the removal of EE(2). The results can provide some useful information for the potential treatment of EE(2) by ozonation in aqueous solution.

Chromatography, High Pressure Liquid↗

Surface ozone measurements at urban coastal site Chennai, in India.

The present study was carried out to gain knowledge of current surface ozone concentrations and the effects of meteorological parameters in the highly populated urban area of Chennai, in South India. We have reported measurement results of surface ozone (O(3)) and meteorological parameters from 17th March to 10th October 2005. A photometric ozone analyzer continuously recorded the ozone concentrations at this site. The present study deals with the statistical characteristics of daily and monthly mean ozone levels under different meteorological conditions. The highest ozone concentrations were recorded in ESE-SE sectors. The monthly mean concentrations were higher in May (23+/-14 ppb) and lower in April at this site (10+/-8 ppb). The maximum hourly ozone concentration reached 69 ppb on 21st April.

Cities↗

Decolorization of methyl orange by ozonation in combination with ultrasonic irradiation.

The combination of ultrasound and ozone for the decolorization of azo dye, methyl orange, was studied. The effect of ultrasonic power, ozone gas flow rate, gaseous ozone concentration, initial dye concentration, pH and hydroxyl radical scavenger on the decolorization of methyl orange was investigated. The results showed that the synergistic effect was achieved by combining ozone with ultrasonic irradiation for the decolorization of methyl orange. The synergistic effect was more significant when the system temperature was raised due to the heat effect of ultrasonic irradiation. The decolorization of methyl orange fits the pseudo first order kinetic model. The decolorization rate increased with the increase of ultrasonic power, ozone gas flow rate, gaseous ozone concentration. However, the decolorization rate decreased with the increasing initial dye concentration. Either pH or sodium carbonate has little effect on the decolorization rate, indicating that the low frequency ultrasound enhanced ozonation process for the decolorization of methyl orange is mainly a direct reaction rather than radical reaction.

Azo Compounds↗

Influences of ozone exposure upon macrophage responsivity to N-formyl-methionyl-leucyl-phenylalanine: mobility and metabolic changes.

Alveolar macrophages represent one of the first lines of cell defence in the lungs. They employ several mechanisms, including phagocytosis and secretion of reactive oxygen and nitrogen species. fMLP, a formylated peptide of bacterial origin, is a potent inducer of phagocyte chemotaxis and is also involved in generating antimicrobial agents such as nitric oxide (NO) and hydrogen peroxide (H2O2). In this study we analysed the in vitro effects of fMLP on the mobility of the THP-1 cell line, which served as a model for alveolar macrophages. Cell mobility and cytotoxicity were also analysed after pre-exposures to an atmosphere polluted with ozone (0.03-0.5 ppm) followed by a fMLP treatment. Finally, the secreted molecules (H2O2 and NO) were measured after ozone exposures ranging from 5 to 30 min and fMLP action. Activation by fMLP alone induced cell movement, whereas pre-exposure to the ozone concentrations decreased it. Addition of fMLP had different effects on cytotoxicity, mobility and metabolite secretion by the cells: (1) cytotoxicity increased depending on ozone concentrations and exposure times; (2) during the first 5 min and for all ozone concentrations, an average decrease of 50% of activated cell mobility was observed; (3) H2O2 was increased, even in combination with ozone; (4) NO was detected at 731 nM, a result that was not affected by ozone pre-exposure.

Air Pollutants↗

Decomposition of aqueous ozone in the presence of aromatic organic solutes.

The decomposition of aqueous ozone is mainly due to the OH(*) radical chain reaction. Some aromatic compounds have been found to tremendously accelerate ozone decomposition in buffered water although their direct reactions with ozone are very low. Hydrogen peroxide has been detected as an important intermediate product in this process. Therefore, a reaction pathway (aromatic ring=>olefin=>H(2)O(2)=>HO(2)(-)) is proposed in this study. Aromatic rings react with OH(*) radicals or ozone to yield olefins. The olefin formed immediately reacts with ozone and is converted to H(2)O(2). Parts of H(2)O(2) dissociate to HO(2)(-), which strongly accelerates aqueous ozone decomposition. Therefore, a new chain reaction appears. The proposed reaction pathway is much faster than another promotion pathway, such as aqueous ozone decomposition promoted by methanol, formic acid or glucose.

Alkenes↗

Mineralization of some natural refractory organic compounds by biodegradation and ozonation.

The objective of this study was to explore the extent of mineralization, reduction in color and reduction of COD of gallic acid, tannin and lignin by ozonation and a combination of aerobic biodegradation and ozonation. Ozonation of pure aliquots (phase I experiments) resulted in the decline in TOC, COD, COD/TOC ratio, UV absorbance at 280 nm and color of the three model compounds investigated, with COD removals of greater than 80% and high removals (>90%) of UV absorbance at 280 nm and color observed in all cases at an ozone dose of 6 mg ozone/mg initial TOC or higher. Aerobic biodegradation of pure gallic acid, tannin and lignin aliquots resulted in COD decline of approximately 36-38%. Subsequent ozonation (phase II experiments) resulted in further decline in TOC, COD, COD/TOC ratio, and increase in UV absorbance at 280 nm and color removals. COD and TOC removals comparable to phase I experiments were obtained with 30-40% lower ozone absorption in phase II experiments. The biodegradation step was quite effective in removing specific UV absorbance at 280 nm, with up to 75% removal observed. Subsequent ozonation increased overall specific UV absorbance at 280 nm to greater than 90%.

Bacteria, Aerobic↗

Integrated ozone and biotreatment of pulp mill effluent and changes in biodegradability and molecular weight distribution of organic compounds.

The overall effectiveness of integrating ozonation with biological treatment on the biodegradability enhancement and recalcitrant organic matter (ROM) removal from pulp mill alkaline bleach plant effluent was investigated. Ozonation was performed in a semi-batch bubble column reactor at pH of 11 and 4.5. Batch biological treatment was conducted in shake flasks. Samples obtained during the treatments were monitored for BOD5, COD, TOC, and molecular weight distribution. At an ozone dosage of 0.7-0.8 mg O3/mL wastewater, integrated treatment showed about 30% higher TOC mineralization compared to individual ozonation or biotreatment. Ozone treatment enhanced the biodegradability of the effluent (monitored as 21% COD reduction and 13% BOD5 enhancement), allowing for a higher removal of pollutants. The conversion of high molecular weight (HMW) to low molecular weight (LMW) compounds was an important factor in the overall biodegradability enhancement of the alkaline effluent. The overall biodegradability of the LMW compounds did not change over the course of ozonation, but it increased from 5% to 50% (measured as COD removal) for the HMW portion. Ozonation at pH of 11 was more effective than that at pH of 4.5 in terms of generating more biodegradable compounds.

Biodegradation, Environmental↗

Ozone treatment and the depletion of detectable pharmaceuticals and atrazine herbicide in drinking water sourced from the upper Detroit River, Ontario, Canada.

The depletion and degradation of pharmacologically active compounds (PhACs) and pesticides as a function of ozonation in drinking water treatment processes is not well studied. The A.H. Weeks drinking water treatment plant (DWTP) serves the City of Windsor, Ontario Canada, and incorporates ozone treatment into the production of drinking water. This DWTP also operates a real-time, scaled down pilot plant, which has two parallel streams, conventional and ozone plus conventional treatments. In this study water samples were collected from key points in the two streams of the pilot plant system to determine the depletion and influence of seasonal changes in water processing parameters on eighteen major PhACs (and metabolites) and seven s-triazines herbicides. However, only carbamazepine (antiepileptic), caffeine (stimulant), cotinine (metabolite of nicotine) and atrazine were consistently detectable in the raw water intake (low to sub-ng/L level). Regardless of the seasonality, the flocculation-coagulation and dual media filtration steps without ozone treatment resulted in no decrease in analyte concentrations, while decreases of 66-100% (undetectable, method detection limits 0.05-1 ng/L) of the analyte concentrations were observed when ozone treatment was part of the water processing. These findings demonstrate that ozone treatment is highly effective in depleting carbamazepine, caffeine, cotinine, and atrazine, and thus is highly influential in the fate of these compounds in drinking water treatment regardless of the seasonal time frame. Currently very few Canadian DWTPs incorporate ozonation into conventional treatment, which suggests that human exposure to these compounds via drinking water consumption may be an issue in affected communities.

Atrazine↗

Calcium enhanced COD removal for the ozonation of phenol solution.

In order to improve the chemical oxygen demand (COD) removal rate for the ozonation of phenol solution, ozonation combined with calcium binding was investigated. The results show that the addition of Ca(2+) can effectively enhance the COD removal rate. During the ozonation, calcium ion can bind with some of the intermediate products of phenol, including high molecular weight products, maleic acid and oxalic acid, to form insoluble precipitates. These calcium binding effects are responsible for the enhancement of COD removal. The variations of ADMI value during ozonation are similar for solutions with and without Ca(2+). However, the peak ADMI value in calcium-contained solution is lower than that without Ca(2+). As the phenol was completely decomposed, the ozone gas outlet concentration rapidly increases. The increasing rate of the ozone gas outlet concentration for ozonation with the presence of Ca(2+) is faster than that without Ca(2+). The optimal initial calcium dosage shows linear relationship with the initial phenol concentration, which is useful for practical application.

Calcium↗

Acute effects of inhaled urban particles and ozone: lung morphology, macrophage activity, and plasma endothelin-1.

We studied acute responses of rat lungs to inhalation of urban particulate matter and ozone. Exposure to particles (40 mg/m3 for 4 hours; mass median aerodynamic diameter, 4 to 5 microm; Ottawa urban dust, EHC-93), followed by 20 hours in clean air, did not result in acute lung injury. Nevertheless, inhalation of particles resulted in decreased production of nitric oxide (nitrite) and elevated secretion of macrophage inflammatory protein-2 from lung lavage cells. Inhalation of ozone (0.8 parts per million for 4 hours) resulted in increased neutrophils and protein in lung lavage fluid. Ozone alone also decreased phagocytosis and nitric oxide production and stimulated endothelin-1 secretion by lung lavage cells but did not modify secretion of macrophage inflammatory protein-2. Co-exposure to particles potentiated the ozone-induced septal cellularity in the central acinus but without measurable exacerbation of the ozone-related alveolar neutrophilia and permeability to protein detected by lung lavage. The enhanced septal thickening was associated with elevated production of both macrophage inflammatory protein-2 and endothelin-1 by lung lavage cells. Interestingly, inhalation of urban particulate matter increased the plasma levels of endothelin-1, but this response was not influenced by the synergistic effects of ozone and particles on centriacinar septal tissue changes. This suggests an impact of the distally distributed particulate dose on capillary endothelial production or filtration of the vasoconstrictor. Overall, equivalent patterns of effects were observed after a single exposure or three consecutive daily exposures to the pollutants. The experimental data are consistent with epidemiological evidence for acute pulmonary effects of ozone and respirable particulate matter and suggest a possible mechanism whereby cardiovascular effects may be induced by particle exposure. In a broad sense, acute biological effects of respirable particulate matter from ambient air appear related to paracrine/endocrine disruption mechanisms.

Animals↗

Accumulated exposure to ozone and measurement of health effects in children and counselors at two summer camps.

In the summer of 1988 a multiorganizational field health study was conducted at two summer day camps in suburban-central New Jersey. Thirty-four campers and counselors had daily pulmonary function tests performed each afternoon while attending camp during the month of July. The subjects ranged from 9 to 35 years of age. A mobile medical screening van was used to house the spirometric equipment and travel to each camp. Continuous ozone measurements were collected over the 19-test day study period. An intense ozone episode was recorded just prior to and during the first 2 weeks of the study. The campers had an increase in respiratory symptoms with increases in ozone concentrations above 120 ppb. Exposures below 120 ppb ozone were not significantly associated with symptoms. Peak expiratory flow rate in children was the only lung function measure associated with increasing ozone concentrations, with an average loss of 4.74 ml/sec/ppb (P-value = 0.05) for the 8-hr ozone exposure measure. Furthermore, it appears that the early intense exposure to ozone produced a persistent decrease in lung function and baseline shift for three days after the episode that obscured the daily dose-response relationship.

Adolescent↗