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Nucleophile assistance of electron-transfer reactions between nitrogen dioxide and chlorine dioxide concurrent with the nitrogen dioxide disproportionation.

The reaction of chlorine dioxide with excess NO(2)(-) to form ClO(2)(-) and NO(3)(-) in the presence of a large concentration of ClO(2)(-) is followed via stopped-flow spectroscopy. Concentrations are set to establish a preequilibrium among ClO(2), NO(2)(-), ClO(2)(-), and an intermediate, NO(2). Studies are conducted at pH 12.0 to avoid complications due to the ClO(2)(-)/NO(2)(-) reaction. These conditions enable the kinetic study of the ClO(2) reaction with nitrogen dioxide as well as the NO(2) disproportionation reaction. The rate of the NO(2)/ClO(2) electron-transfer reaction is accelerated by different nucleophiles (NO(2)(-) > Br(-) > OH(-) > CO(3)(2-) > PO(4)(3-) > ClO(2)(-) > H(2)O). The third-order rate constants for the nucleophile-assisted reactions between NO(2) and ClO(2) (k(Nu), M(-2) s(-1)) at 25.0 degrees C vary from 4.4 x 10(6) for NO(2-) to 2.0 x 10(3) when H(2)O is the nucleophile. The nucleophile is found to associate with NO(2) and not with ClO(2) in the rate-determining step to give NuNO(2)(+) + ClO(2)(-). The concurrent NO(2) disproportionation reaction exhibits no nucleophilic effect and has a rate constant of 4.8 x 10(7) M(-1) s(-1). The ClO(2)/NO(2)/nucleophile reaction is another example of a system that exhibits general nucleophilic acceleration of electron transfer. This system also represents an alternative way to study the rate of NO(2) disproportionation.

Journal Article↗

Nitrate reductase activity of needles of Norway spruce fumigated with different mixtures of ozone, sulfur dioxide, and nitrogen dioxide.

Four-year-old spruce clones (Picea abies (L.) Karst.) cultivated in sand and provided with a complete nutrient solution, or a solution deficient in magnesium and calcium, were exposed to the pollutant mixtures SO(2)/NO(2), O(3)/NO(2), and O(3)/SO(2)/NO(2), at realistic concentrations for 32 weeks. Fumigation caused a slight increase of total N contents in current year needles, whereas in one-year-old needles N concentrations did not change. The response of nitrate reductase activity to pollutant stress depended on needle age and nutrient supply, respectively. In one-year-old needles fumigation resulted in a significant inhibition of enzyme activity, particularly in Mg and Ca deficient trees. The combination of all three components proved to be most effective in causing a decrease by 60% compared to the control. In contrast, nitrate reductase activity was stimulated in current year needles, especially by O(3)/NO(2) and O(3)/SO(2)/NO(2). Changes in the activity of nitrate and nitrite reductases are considered as a factor contributing to the high phytotoxic potential of pollutant combinations with NO(2).

Journal Article↗

The effects of prior exposure to sulphur dioxide and nitrogen dioxide on the water relations of timothy grass (Phleum pratense) under drought conditions.

Studies of the growth and water relations of the grass Phleum pratense L. (Timothy) were made after simultaneous exposure to SO(2) and NO(2) at concentrations ranging from 80 + 57.4 microg m(-3) to 240 + 172.2 microg m(-3) (SO(2) + NO(2)). Decreased partitioning to the roots was evident during exposure to the pollutants, but when the plants were returned to clean air restrictions in root growth did not persist. Shoot to root partitioning was, however, complicated by the additional factor of changes in the nutritional status of the soil after additional columns of fresh soil were attached to the original tubes. The rate of use of soil water was nevertheless substantially increased by the pollution treatment and after a period of 23 days in which water was withheld, a clear pollution x water stress interaction was seen. The ability of polluted leaves to conserve water under severe water stress was tested by excising the leaves and measuring their water loss over time. The results from this second experiment showed that conservation of water by the leaves was appreciably affected after exposure to 80 + 57.4 microg m(-3) or 133.3 + 95.6 microg m(-3) SO(2) + NO(2). It seems likely that damage to the cells in the epidermal layer, leading to malfunctioning of stomata, is mainly responsible for the reduced ability to conserve water under conditions of extreme stress.

Journal Article↗

Nitrogen dioxide and respiratory illness in children. Part II: Assessment of exposure to nitrogen dioxide.

Repeated measurements of nitrogen dioxide were obtained from 1988 to 1991 in the homes of 1,205 infants living in Albuquerque, NM. Passive diffusion samplers were used to obtain a series of two-week integrated measurements from the home of each infant for use in a cohort study of the relation of residential exposure to nitrogen dioxide and respiratory illnesses. Information on stove use and time spent inside the residence was collected at two-week and two-month intervals, respectively. During the winter, in the bedrooms of homes with gas cooking stoves, mean nitrogen dioxide concentrations were 21 parts per billion (ppb); mean concentrations in the living room and kitchen were 29 ppb and 34 ppb, respectively. In homes with electric cooking stoves, the mean bedroom concentration was 7 ppb during the winter. Lower indoor concentrations were observed during the summer in homes with both gas and electric stoves. On average, infants spent approximately 12.3 hours per day in their bedrooms, 7.3 hours in the living rooms, 35 minutes in the kitchens, and 3.8 hours out of their homes. (As a condition of participation, none of the infants spent more than 20 hours per week in day care outside of their homes). The mean time infants spent in the kitchen during cooking was approximately nine minutes per day. We tested whether exposures of infants living in homes with gas stoves could be reasonably estimated by measurements in the bedroom in comparison with time-weighted average concentrations based on time-activity data and simultaneous nitrogen dioxide measurements in the kitchen, living room, and bedroom. In 1,937 two-week intervals from 587 infants, 90% of time-weighted exposure (on the three-level classification used in this study) estimates were in agreement with estimates based on bedroom concentrations alone. The agreement of the time-weighted nitrogen dioxide exposure estimates with the bedroom concentrations is attributed to limited amounts of cooking stove use (the mean was 29 minutes per day), small room-to-room differences in nitrogen dioxide concentrations (the mean kitchen-bedroom difference was 12 ppb), and the relatively large proportion of time that infants spent in their bedrooms.

Air Pollution, Indoor↗

Passive colorimetric dosimeter tubes for ammonia, carbon monoxide, carbon dioxide, hydrogen sulfide, nitrogen dioxide and sulfur dioxide.

Colorimetric, stain length, personal dosimeters operating by gas diffusion have been developed to determine worker exposure for up to an eight-hour period for several inorganic airborne contaminants in the range of their Threshold Limit Values. Length of stain, colorimetric dosimeters have been made for the detection of ammonia (NH3), carbon monoxide (CO), carbon dioxide (CO2), hydrogen sulfide (H2S), nitrogen dioxide (NO2), and sulfur dioxide (SO2) in air. For each gas detection system, the sampler depends on the transfer of the gas by diffusion into a glass tube containing a colorimetric length of stain indicator. The stain length developed in a given period of time is compared to a calibration chart to determine, on the spot, the average gas concentration to which the dosimeter has been exposed. These dosimeters are known by the trade name Vapor Gard.

Air Pollutants, Occupational↗

Nitrogen dioxide, the oxides of nitrogen, and infants' health symptoms. ALSPAC Study Team. Avon Longitudinal Study of Pregnancy and Childhood.

In this cross-sectional postal study, the authors measured nitrogen dioxide levels inside infants' bedrooms and outside their homes. During the 2-wk monitoring period, the authors investigated the association between nitrogen dioxide levels and 20 infant symptoms. The subjects were 1,200 women who had infants aged 3-12 mo. Median levels of indoor and outdoor nitrogen dioxide were 6.8 and 12.6 ppb, respectively. Environmental factors that were associated significantly with indoor levels were gas cooking, cigarette smoking, reported traffic levels, and presence of a kerosene heater; use of a cooker hood was associated negatively with indoor nitrogen dioxide levels. There was no evidence for any short-term significant association between prevalence of respiratory symptoms and nitrogen dioxide levels. Diarrhea, the only symptom associated significantly and positively with indoor nitrogen dioxide levels, had unadjusted and adjusted odds ratios of 1.48 (95% confidence interval: 1.13, 1.95) and 1.38 (1.11, 1.70), respectively. This association is discussed in terms of a proposed mechanism with nitric oxide. No association between a gas cooker in the home and diarrhea was found. The association between diarrhea and nitrogen dioxide level might have been a chance finding; the authors investigated 20 symptoms, and at least 1 was expected to be significant at the .05 level. The finding, however, was similar to that reported in a previous study in which a gas cooker was a proxy for nitrogen dioxide exposure.

Adult↗

Effect of nitrogen dioxide and sulphur dioxide on airway response of mild asthmatic patients to allergen inhalation.

Air pollution may enhance the airway response of asthmatic subjects to allergen inhalation. To test the hypothesis that sulphur dioxide and nitrogen dioxide alone or in combination could have a contributory role, we have studied the effect of 6 h exposure to air, 200 parts per billion (ppb) sulphur dioxide, 400 ppb nitrogen dioxide, and the two gases together on the airway response to inhaled allergen in ten volunteers with mild atopic asthma. The subjects were exposed to the gases in random order at weekly visits, then challenged with pre-determined concentrations of Dermatophagoides pteronyssinus allergen 10 min after each exposure. The forced expiratory volume in 1 s (FEV1), forced vital capacity (FVC), and cumulative breath units (CBU) of D pteronyssinus allergen required to produce a 20% fall in FEV1 (PD20FEV1) were measured after each exposure. Compared with air, neither sulphur dioxide nor nitrogen dioxide nor the combination significantly altered FEV1 or FVC. Although the decreases in PD20FEV1 after exposure to each agent alone were not significant (41.2%, p = 0.125 after nitrogen dioxide; 32.2%, p = 0.506 after sulphur dioxide) the decrease after exposure to the combination was significant (60.5 [SE 8.1]%, p = 0.015). Exposure to a combination of sulphur dioxide and nitrogen dioxide in concentrations that could be encountered in heavy traffic enhances the airway response to inhaled allergen, possibly as a result of previous airway inflammation.

Adult↗

Studies on biochemical effects of nitrogen dioxide: I. Lipid peroxidation as measured by ethane exhalation of rats exposed to nitrogen dioxide.

This research was in order to follow the periodic fluctuation of lipid peroxidation by a new method in rats exposed to nitrogen dioxide. Wistar male rats were examined for lipid peroxidation as demonstrated by ethane exhalation. In rats continuously exposed to 10 ppm nitrogen dioxide for 2 weeks, the amount of ethane exhaled fluctuated in a complex manner during the exposure. Ethane exhalation decreased slightly after the first day of exposure and then increased rapidly. The maximal values were observed after the fourth day of exposure and then decreased gradually to the initial level. Furthermore, the activity of glutathione peroxidase in lungs of rats exposed to 10 ppm nitrogen dioxide varied symmetrically against the change of ethane formation. Similar changes in ethane exhalation were observed in rats exposed to the lowest levels of nitrogen dioxide (0.4, 1.2 and 4.0 ppm) for 4 months. Compared to 10 ppm nitrogen dioxide exposure for 14 days, the characteristics in rats exposed to the low levels (0.4-4.0 ppm) of nitrogen dioxide were: the decline of ethane formation, the delay in alterations, and the tendency toward gradual increase during the longer period exposure.

Animals↗

Atmospheric conversion of sulfur dioxide to particulate sulfate and nitrogen dioxide to particulate nitrate and gaseous nitric acid in an urban area.

Sulfur dioxide, nitrogen dioxide, particulate sulfate and nitrate, gaseous nitric acid, ozone and meteorological parameters (temperature and relative humidity) were measured during the winter season (1999-2000) and summer season (2000) in an urban area (Dokki, Giza, Egypt). The average particulate nitrate concentrations were 6.20 and 9.80 microg m(-3), while the average gaseous nitric acid concentrations were 1.14 and 6.70 microg m(-3) in the winter and summer seasons, respectively. The average sulfate concentrations were 15.32 microg m(-3) during the winter and 25.10 microg m(-3) during the summer season. The highest average concentration ratio of gaseous nitric acid to total nitrate was found during the summer season. Particulate sulfate and nitrate and gaseous nitric acid concentrations were relatively higher in the daytime than those in the nighttime. Sulfur conversion ratio (Fs) and nitrogen conversion ratio (Fn) defined in the text were calculated from the field measurement data. Sulfur conversion ratio (Fs) and nitrogen conversion ratio (Fn) in the summer were about 2.22 and 2.97 times higher than those in the winter season, respectively. Moreover, sulfur conversion ratio (Fs) and nitrogen conversion ratio (Fn) were higher in the daytime than those in the nighttime during the both seasons. The sulfur conversion ratio (Fs) increases with increasing ozone concentration and relative humidity. This indicates that the droplet phase reactions and gas phase reactions are important for the oxidation of SO2 to sulfate. Moreover, the nitrogen conversion ratio (Fn) increases with increasing ozone concentration, and the gas phase reactions are important and predominant for the oxidation of NO2 to nitrate.

Air Pollutants↗

Pro-inflammatory responses of human bronchial epithelial cells to acute nitrogen dioxide exposure.

Nitrogen dioxide (NO2) is an environmental oxidant, known to be associated with lung epithelial injury. In the present study, cellular pro-inflammatory responses following exposure to a brief high concentration of NO2 (45 ppm) were assessed, using normal human bronchial epithelial (NHBE) cells as an in vitro model of inhalation injury. Generation and release of pro-inflammatory mediators such as nitric oxide (NO), IL-8, TNF-alpha, IFN-gamma and IL-1beta were assessed at different time intervals following NO2 exposure. Effects of a pre-existing inflammatory condition was tested by treating the NHBE cells with different inflammatory cytokines such as IFN-gamma, IL-8, TNF-alpha, IL-1beta, either alone or in combination, before exposing them to NO2. Immunofluorescence studies confirmed oxidant-induced formation of 3-nitrotyrosine in the NO2-exposed cells. A marked increase in the levels of nitrite (as an index of NO) and IL-8 were observed in the NO2-exposed cells, which were further enhanced in the presence of the cytokines. Effects of various NO inhibitors combined, with immunofluorescence and Western blotting data, indicated partial contribution of the nitric oxide synthases (NOSs) toward the observed increase in nitrite levels. Furthermore, a significant increase in IL-1beta and TNF-alpha generation was observed in the NO2-exposed cells. Although NO2 exposure alone did induce slight cytotoxicity (<12%), but presence of inflammatory cytokines such as TNF-alpha and IFN-gamma resulted in an increased cell death (28-36%). These results suggest a synergistic role of inflammatory mediators, particularly of NO and IL-8, in NO2-mediated early cellular changes. Our results also demonstrate an increased sensitivity of the cytokine-treated NHBE cells toward NO2, which may have significant functional implications in vivo.

Blotting, Western↗

[Short-term effect of air pollution with sulphur dioxide, black smoke and nitrogen dioxide on mortality of urban Polish population].

The paper presents results of analysis of short-term effect of atmospheric air pollution with sulphur dioxide (SO2), suspended particles (BS) and nitrogen dioxide (NO2) for daily number of death from all causes (without external), from diseases of cardiovascular and respiratory diseases and from malignant neoplasms in four Polish cities Kraków, Lódź, Poznań and Wrocław. Analysis was carried out using modern methods of statistical modeling--generalized additive models. Potential confounding factors (long-term changes of mortality, day of week, meteorological conditions, national and summer holidays and periods of influenza epidemics) were taken into account during model building process. Results for every city and from meta-analysis are presented. Statistically significant increase of mortality from all causes was associated with increase in all investigated air pollutants.

Air Pollutants↗

Nitrogen dioxide and respiratory illness in children. Part IV: Effects of housing and meteorologic factors on indoor nitrogen dioxide concentrations.

In a prospective study of infants' exposure to nitrogen dioxide (NO2)* and respiratory illness, NO2 concentrations were measured in more than 1,400 homes in Albequerque, NM, From January 1988 through June 1991 (Health Effects Institute Research Report Number 58, Parts I, II and III). This report characterizes the variability in indoor NO2 concentrations across seasons and years, and identifies factors associated with variation in concentrations between homes and across seasons. In regression analyses of winter data, NO2 levels in the infants' bedrooms were predominately determined by the presence of gas cooking ranges with continuously burning pilot lights, the presence of wall or floor furnaces, the use of the stove for space heating, and the square footage of the living space. These findings are consistent with previously published analysis of data from homes in other U.S. cities. Relatively small differences in seasonal NO2 levels were observed across years. The correlation coefficient (r) of bedroom NO2 levels obtained in the same homes was 0.66 over two winters and 0.48 over two summers. For homes that had gas cooking ranges with continuously burning pilot lights, the NO2 bedroom concentrations differed, on average, less than 5 parts per billion (ppb) across winters. These differences were hypothesized to be caused by differences in the use of indoor NO2 sources, ventilation, and ambient (outdoor) NO2 levels. We were, however, unable to demonstrate an association between year-to-year differences in seasonal indoor NO2 concentrations and reported use of cooking range, furnace, or heater, or ambient NO2 levels, or temperature.

Air Pollution, Indoor↗

Susceptibility to virus infection with exposure to nitrogen dioxide.

The interaction between nitrogen dioxide (NO2) exposure and human susceptibility to respiratory virus infection was investigated in a placebo-controlled, randomized, blinded trial that was conducted in an environmentally controlled research chamber over a three-year period. Healthy, non-smoking volunteers, 18 to 35 years old, who were seronegative to influenza A/Korea/82 (H3N2) virus, were randomly assigned either to breathe filtered clean air (clean air group) or nitrogen dioxide (exposure group) for two hours a day for three consecutive days. The nitrogen dioxide concentrations were 2 ppm (Year 1), 3 ppm (Year 2), and 1 or 2 ppm (Year 3). Live, attenuated cold-adapted (ca) influenza A/Korea/82 reassortant virus was administered intranasally to all subjects after the second day of exposure. Only one of the 152 volunteers had any symptoms, and that subject had only a low-grade fever. No adverse changes in pulmonary function or nonspecific airway reactivity to methacholine were observed after 2 or 3 ppm nitrogen dioxide exposure, virus infection, or both. Infection was defined by virus recovery, a four-fold or greater increase in serum or nasal wash influenza-specific antibody titers, or both. The infection rates of the groups exposed to nitrogen dioxide and those breathing clean air were: 12/21 (2 ppm nitrogen dioxide) versus 15/23 (clean air) in Year 1; 17/22 (3 ppm nitrogen dioxide) versus 15/21 (clean air) in Year 2; and 20/22 (2 ppm nitrogen dioxide) and 20/22 (1 ppm nitrogen dioxide) versus 15/21 (clean air) in Year 3. Although the differences were not statistically significant, the groups exposed to 1 or 2 ppm nitrogen dioxide in the last year became infected more often (91 percent) than those breathing clean air (71 percent). The frequencies of infection in two of the four groups exposed to nitrogen dioxide were higher than the 56 to 73 percent infection rate observed in previous studies in healthy human volunteers with the same dose of ca-influenza A (H3N2) virus. Our findings suggest, but do not prove, that nitrogen dioxide alone may play a role in increasing the susceptibility of adults to respiratory virus infections.

Adolescent↗

Respiratory symptoms in children and indoor exposure to nitrogen dioxide and gas stoves.

Nitrogen dioxide levels were measured in 80 homes in the Latrobe Valley, Victoria, Australia, using passive samplers. Some 148 children between 7 and 14 yr of age were recruited as study participants, 53 of whom had asthma. Health outcomes for the children were studied using a respiratory questionnaire, skin prick tests, and peak flow measurements. Nitrogen dioxide concentrations were low, with an indoor median of 11.6 microgram/m3 (6.0 ppb), and a maximum of 246 microgram/m3 (128 ppb). Respiratory symptoms were more common in children exposed to a gas stove (odds ratio 2.3 [95% CI 1. 0-5.2], adjusted for parental allergy, parental asthma, and sex). Nitrogen dioxide exposure was a marginal risk factor for respiratory symptoms, with a dose-response association present (p = 0.09). Gas stove exposure was a significant risk factor for respiratory symptoms even after adjusting for nitrogen dioxide levels (odds ratio 2.2 [1.0-4.8]), suggesting an additional risk apart from the average nitrogen dioxide exposure associated with gas stove use. Atopic children tended to have a greater risk of respiratory symptoms compared with nonatopic children with exposure to gas stoves or nitrogen dioxide, but the difference was not significant.

Adolescent↗

Isotonic smooth muscle response in human bronchi exposed in vitro to nitrogen dioxide.

Exposure to nitrogen dioxide (NO2), a common oxidant airborne pollutant, has been shown to cause reversible effects on lung function and airway responsiveness, in addition to airways inflammation. However, there have been conflicting reports concerning NO2-induced airway hyperresponsiveness. In the present study, we investigated the isotonic smooth muscle response in isolated human bronchi previously exposed in vitro to NO2. Bronchial segments were obtained from 12 patients who had undergone thoracotomy for lung cancer. Bronchial segments from each patient were exposed to air and to 2.5 parts per million (ppm) NO2 for 4 h. The contractile response of bronchial rings to acetylcholine, neurokinin A (NKA), and substance P was then studied under isotonic conditions. The response to NKA was also studied in rings, with or without epithelium, exposed either to air or 7 ppm NO2. No NO2-induced alteration of the bronchial smooth muscle isotonic response was found under any of the experimental conditions. We conclude that in vitro exposure to up to 7 ppm nitrogen dioxide does not cause alterations of the human bronchial smooth muscle shortening capacity.

Acetylcholine↗

Indoor nitrogen dioxide and childhood respiratory illness.

Nitrogen dioxide is produced from the combustion of fossil fuels and as an emission from gas-fired appliances, and is also a component of tobacco smoke. Nitrogen dioxide has been shown in experimental animals to be toxic to the respiratory tract. A n number of recent studies have suggested that children exposed to significant levels of nitrogen dioxide in the home may be more susceptible to respiratory illness than children exposed to normal ambient levels. Respiratory illness is a major cause of morbidity in children everywhere. Here, we review the available evidence of this association and explore methodological issues in measurement of nitrogen dioxide exposure--misclassification of subjects, symptom bias and confounding. It has recently been shown that some New South Wales school rooms, where unflued gas heaters are often used as a source of warmth, have nitrogen dioxide levels which are above recommended ambient levels for outside air. This has underlined the need for setting standards for indoor levels of various pollutants, and cohort studies are suggested, to include personal monitoring and prospective data collection techniques.

Air Pollution, Indoor↗