World-wide ambient measurements of peroxyacetyl nitrate (PAN) and implications for plant injury

Peroxyacetyl nitrate (PAN) is a major phytotoxic component of the photochemical oxidant complex in southern California, but its distribution and effects in other parts of the world are very poorly understood. Based on ambient air sampling at Riverside, California, in 1980, and published reports of PAN concentrations from other parts of the world, PAN concentrations in southern California appear to be five to ten times higher than those reported from eastern North America, western Europe, or Japan. PAN in Riverside, California, averaged 8.1 ppb in July, 9.4 ppb in September and 8.8 ppb in October 1980. These values represent the average of 48 measurements made at 15-min intervals between 0800 and 2000 LT. Potentially phytotoxic episodes, defined herein as PAN > 15 ppb for 4 h during the a.m. period or > 25 ppb for 4h in the p.m. period occurred 27 times in Riverside in 1980. These data were similar to PAN concentrations recorded in the mid 1960s in the Los Angeles Basin, indicating that PAN continues to be a serious air pollution problem in southern California. In contrast, PAN normally averages 1 ppb or less outside of southern California, and because of this low concentration, PAN by itself does not appear to be a major cause of photochemical oxidant injury to vegetation in those regions.     

Peroxyacetyl nitrate and peroxypropionyl nitrate in Porto Alegre,Brazil

For 41 days between 25 May 1996 and 27 March 1997, peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) have been measured by electron capture gas chromatography at Santa Rita near Porto Alegre, RS, Brazil, where light-duty vehicles used either ethanol or a gasoline–MTBE blend. Daily maximum concentrations ranged from 0.19 to 6.67 ppb for PAN and 0.06 to 0.72 ppb for PPN. Linear regression of maximum PPN vs. maximum PAN yielded a slope of 0.105±0.004 (R²=0.974). Diurnal variations of ambient PAN often followed those of ozone with respect to time of day but not with respect to amplitude. This was reflected in the large relative standard deviations associated with the study-averaged PAN/ozone concentration ratio, 0.037±0.105 (ppb/ppb, n=789) and the maximum PAN/maximum ozone concentration ratio, 0.028±0.015 (ppb/ppb, range 0.005–0.078, n=41). On several days PAN accounted for large fractions of the total ambient NO_x in the late morning and afternoon hours, e.g., PAN/NO_x⩽0.58 and PAN/(NO_x–NO) ⩽0.76 on 27 March 1997. The amount of PAN lost by thermal decomposition (TPAN) was comparable in magnitude to that present in ambient air. The ratios TPAN/(PAN+TPAN) were up to 0.53, 0.67 and 0.64 during the warm afternoons of 25, 26 and 27 March 1997, respectively. The highest calculated value of TPAN was 5.6 ppb on 27 March 1997. On that day the 24 h-averaged value of TPAN (1.01 ppb) was nearly the same as that of PAN (1.09 ppb). Using computer kinetic modeling (SAPRC 97 chemical mechanism) and sensitivity analysis of VOC incremental reactivity, we ranked VOC present in Porto Alegre ambient air for their importance as precursors to PAN and to PPN. Using as input data the averages of VOC concentrations measured in downtown Porto Alegre during the ca. 1 yr period March 1996–April 1997, we calculated that the most important precursors to PAN and PPN were the SAPRC 97 model species ARO2 (which includes the aromatics xylenes, trimethylbenzenes, ethyltoluenes, etc.), which accounted for ca. 17% of the total PAN and total PPN formation potentials. Overall, the results indicate a major role for aromatics and alkenes and a minor role for acetaldehyde and ethanol as precursors to peroxyacyl nitrates in the Porto Alegre urban area.     

Peroxyacetyl Nitrate-Induced Inhibition of Cell Wall Metabolism

Levels of PAN which inhibit oat coleoptile section growth reversibly, severely inhibit metabolism of cellulose and of cell wall noncellulosic polysaccharides. An enzyme in the coleoptile cell walls which hydrolyzes some of the noncellulosic glucan was partially inactivated by direct PAN treatment of homogenized cell wall. Treatment of intact cells by PAN also resulted in a partially inactivated enzyme. Coleoptile phos-phoglucomutase was partially inactivated by treatment with PAN both in vitro and in vivo. After treatment of intact cells with PAN, phosphoglucomutase associated with subcellular particles was more severely inactivated than was soluble enzyme. Uridine diphosphate glucose pyrophosphorylase from coleoptiles was inactivated by PAN in vitro but not in vivo. A particulate cellulose synthetase from coleoptiles was inactivated by PAN both in vitro and in vivo. Since cell wall biosynthesis and or degradation are needed for expansion it is concluded that PAN inhibition of these enzymes may account for reduced cell growth. The work of Dr. Morris J. Garber who carried out the analysis of variance is gratefully acknowledged.     

Peroxyacetylnitrate (PAN) in the atmosphere of Edmonton,Alberta, Canada

Peroxyacetyl nitrate (PAN) concentrations were measured from December 1982 to May 1984 in downtown Edmonton, Alberta, as well as upwind and downwind of the city. The highest PAN concentration recorded in Edmonton was 7.5 ppb, and the mean daily maximum was 0.6 ppb. Maximum PAN and ozone concentrations were often reached in the early afternoon but there were many exceptions, with maxima as early as 0900 MST and as late as 2000 MST. PAN often persisted throughout the night in Edmonton, whereas in Calgary it disappeared rapidly in the evening. Edmonton PAN concentrations showed seasonal variation and were limited in the wintertime by the lack of solar radiation and in the summer by the low concentration of pollutants. PAN episodes were highly correlated with the presence of anticyclonic synoptic disturbances (ridges) in the upper air flow. Surface synoptic conditions varied but weak pressure gradients were common to all episodes. Seasonal and diurnal variations of PAN are discussed in relation to observations from Calgary, Alberta; Los Angeles, CA; and other North American cities.     

Physiological and Biochemical Effects of Atmospheric Oxidants on Plants

Photochemically produced oxidants in the atmosphere cause injury to plants primarily through inhibition of basic metabolic processes. Plants vary in their response to the oxidants and this variation must be dependent in part on the variation in metabolic activity with age or environmental conditions for growth, to a large degree not understood. Data are presented in this paper to show: (1) The changes in permeability of leaf tissue to exogenous substrate and in catabolic utilization of this substrate after exposure of plants to ozone but before visible symptoms appear; (2) The change in leaf carbohydrates as a result of exposure to ozone; (3) The protective effect of red light (700 mμ) during exposure of bean plants to peroxyacetyl nitrate (PAN); (4) The correlation of sulfhydryl (SH) content in bean leaf tissue with age of plants and light regime; and (5) Effect of light regime and age of plants on incorporation of C¹⁴ from C¹⁴-PAN by bean leaf tissue.     

Foliar injury, leaf gas exchange and biomass responses of black cherry (Prunus serotina Ehrh.) half-sibling families to ozone exposure

Open pollinated families of black cherry seedlings were studied to determine genotypic differences in foliar ozone injury and leaf gas exchange in 1994 and growth response following three growing seasons. An O(3)-sensitive half-sibling family (R-12) and an O(3)-tolerant half-sibling family (MO-7) planted in natural soil were studied along with generic nursery stock (NS) seedlings. Ozone exposure treatments were provided through open top chambers and consisted of 50, 75, and 97% of ambient ozone, and open plots from May 9 to August 26, 1994. Ambient ozone concentrations reached an hourly peak of 88 ppb with 7-hour averages ranging from 39 to 46 ppb. Seedlings in the 50 and 75% of ambient chambers were never exposed to greater than 80 ppb O(3). Visible foliar ozone injury (stipple) was significantly higher for R-12 seedlings than MO-7 seedlings and increased with increasing ozone exposures. For the chamber treatments averaged over all families, there was no significant difference in stomatal conductance and net photosynthetic rates, but there was a significant decrease in root biomass, and a significant decrease in root/shoot ratio between the 50 and 97% of ambient chambers. Stomatal conductance and net photosynthetic rates were significantly different between families with R-12 seedlings generally greater than MO-7 seedlings. The R-12 seedlings had a 7.5 mmol m(-2) increase in ozone uptake compared to MO-7, and at the same cumulative O(3) exposure R-12 exhibited 40.9% stippled leaf area, whereas MO-7 had 9.2% stippled leaf area. Significant differences were observed in stem volume growth and total final biomass between the open-top chambers and open plots. Although R-12 had the most severe foliar ozone injury, this family had significantly greater stem volume growth and total final biomass than MO-7 and NS seedlings. Root:shoot ratio was not significantly different between MO-7 and R-12 seedlings.     

Measurements of peroxyacyl nitrates (PANS) in Mexico City: implications for megacity air quality impacts on regional scales

Peroxyacyl nitrates (PANs) were measured using gas chromatography with electron capture detection (GC/ECD) in north central Mexico City during February–March of 1997. Peroxyacetyl nitrate (PAN) was observed to exceed 30 ppb during five days of the study, with peroxypropionyl nitrate (PPN) and peroxybutryl nitrate (PBN) reaching 6 and 1 ppb maximum, respectively. Levels of total PANs typically exceeded 10 ppb during the period of measurement and showed a very strong diurnal variation with PANs maximum during the early afternoon and falling to less than 0.1 ppb during the evening hours. These levels of PANs are the highest reported values in North America (and the world) for an urban center, since levels of approximately 30 ppb were reported during the late 1970s in the Los Angeles area (South Coast Air Basin, Tuazon et al., 1978). Hydrocarbon measurements indicate that the levels of olefins, specifically butenes are significant in Mexico City. A time series taken of source indicator hydrocarbons taken before and during a Mexican National Holiday with reduced automobile traffic clearly show that mobile sources of butenes are as important as liquefied petroleum gas. Observations of 10–40 ppb C methyl-t-butyl ether (MTBE) are consistent with MTBE/gasoline fuel usage as a source of isobutene and formaldehyde. Both these reactive species can lead to increased oxidant and PAN formation. The strong diurnal profiles of PANs are consistent with regional clearing of the Mexico City air basin on a daily basis. Estimates are given using a simple box model calculation for a number of key primary and secondary pollutant emissions from this megacity on an annual basis. These calculations indicate that megacities can be important sources of both primary and secondary pollutants, and that PANs produced in megacity environments are likely to contribute strongly to regional scale ozone and aerosol productions during long range transport.     

Suitability of Nicotiana tabacum 'Bel W3' for biomonitoring ozone in São Paulo, Brazil

Nicotiana tabacum 'Bel W3' is a widely used sensitive bioindicator for ambient ozone, but it is rarely used in tropical countries. Our goal was to determine the suitability of this plant for biomonitoring ozone in the city of S?o Paulo by evaluating the relationships between leaf necroses and ozone under field conditions and measurements of chlorophyll a fluorescence and antioxidants in plants exposed to different concentrations of ozone in closed chambers. While a weak linear relationship between leaf injury and ozone concentrations (R(2)=0.10) was determined in the field, a strong linear relationship was observed in the chamber experiments. Maximum leaf injury was observed in plants submitted to 40 ppb, which coincided with a significant decrease in fluorescence and total ascorbic acid. The relationship between leaf damage observed in the field and ozone was improved when the concentrations were limited to 40 ppb (R(2)=0.28).     

A sodium carbonate coated denuder for determination of nitrous acid in the atmosphere

A denuder technique for sampling and analysing nitrous acid at sub ppb levels in air is described. After sampling, the sodium carbonate coated denuder is leached in water, and the NO⁻₂ concentration is determined spectrophotometrically. Field tests show that PAN is partly sorbed and hydrolized to nitrite in the sodium carbonate layer. It seems as HNO₂ also can be formed by heterogeneous reactions between NO and NO₂ at the denuder wall. These sampling artifacts were overcome by sampling with two or three denuders in series. The presence of PAN deteriorates the detection limit, which during optimal conditions is about 0.5 nmole m⁻³ (0.01 ppb). The method is therefore not recommended for measurements in background air, where HNO₂ concentrations normally are low compared to PAN concentrations.     

Effects of ozone on chlorophyll and quantum yield of tobacco (Nicotiana tabacum L.) varieties

Plants of Bel-W3 and of seven commercial tobacco varieties (Nicotiana tabacum L.) were exposed to two relatively low ozone concentrations (90 or 135 ppb) for 20 consecutive days, for 8 h per day. Ozone caused necrotic and chlorotic spots, acceleration of leaf senescence, depression of photosynthetic mechanism, chlorophyll diminution and greater destruction of chl a than of chl b. The higher sensitivity of chl a was also confirmed by exposure of segments of leaves in test tubes to high ozone concentration (>1000 ppb) as well as by bubbling of ozone in extracts of chlorophyll in vitro. The quantum yield (QY) of photosynthesis was positively correlated with the chlorophyll content and negatively correlated with the visible injury and the chl b/a ratio.     

Photochemical Pollution at Two Southern California Smog Receptor Sites

A one-year survey of air quality has been carried out at two southern California inland locations, Perris and Palm Springs (90 km E-SE and 120 km E of Los Angeles) to evaluate transport of photochemical smog from the Los Angeles area and to assess population exposure to toxic air pollutants in the Coachella Valley and eastern Riverside County. Air pollutants measured included formaldehyde, acetaldehyde, nitric acid, and peroxyacetyl nitrate (PAN). Acetic acid was also measured as part of the time-integrated method employed to measure PAN. In addition, intensive studies were carried out at both locations and included measurements of aldehydes, nitric acid, PAN, peroxypropionyl nitrate (PPN), methylchloroform and tetrachloroethylene.

Maximum concentrations of HCHO, CH₃CHO, HNO₃, PAN, PPN, CH₃COOH and C₂CI₄ were 26, 21, 4.5, 7.6, 0.42, 6.6 and 0.29 ppb in Palm Springs and 15, 30, 6.3, 9.1, 0.73, 7.8 and 0.43 ppb in Perris. Pollutant concentrations measured in Palm Springs and Perris are compared to those measured in the Los Angeles area, and are discussed in terms of formation and removal during transport.     

Ozone exposure thresholds and foliar injury on forest plants in Switzerland

Canton Ticino in southern Switzerland is exposed to some of the highest concentrations of tropospheric ozone in Europe. During recent field surveys in Canton Ticino, foliar symptoms identical to those caused by ozone have been documented on native tree and shrub species. In Europe, the critical ozone level for forest trees has been defined at an AOT40 of 10 ppm.h O3 (10 ppm.h accumulated exposure of ozone over a threshold of 40 ppb) during daylight hours over a six-month growing season. The objective of this study was to determine the amount of ambient ozone required to induce visible foliar symptoms on various forest plant species in southern Switzerland. Species were grown within eight open-top chambers and four open plots at the Vivaio Lattecaldo Cantonal Forest Nursery in Ticino, Switzerland. Species differed significantly in terms of the ppb.h exposures needed to cause visible symptoms. The most to least symptomatic species grown within open-plots in this study rank as Prunus serotina, Salix viminalis, Vibrnum lantana, Rhamnus cathartica, Betula pendula, Rumex obtusifolius, Sambucus racemosa, Morus nigra, Prunus avium, Fraxinus excelsior, Rhamnus frangula, Alnus viridis, Fagus sylvatica and Acer pseudoplatanus. Similar rankings were obtained in the non-filtered chamber plots. The ranking of species sensitivity closely follows AOT values for the occurrence of initial symptoms and symptom progression across the remainder of the exposure season. Species that first showed evidence of foliar injury also demonstrated the most sensitivity throughout the growing season, with symptoms rapidly advancing over ca. 25-30% of the total plant leaf surfaces by the end of the observation period. Conversely, those species that developed symptoms later in the season had far less total injury to plant foliage by the end of the observation period (1.5 to < 5% total leaf area injured). The current European ambient ozone standard may be insufficient to protect native plant species from visible foliar injury, and many more native species may be sensitive to ozone-induced foliar injury than are currently known.     

Tibouchina pulchra (Cham.) Cogn., a native Atlantic Forest species, as a bio-indicator of ozone: visible injury

Tibouchina pulchra saplings were exposed to carbon filtered air (CF), ambient non-filtered air (NF) and ambient non-filtered air+40 ppb ozone (NF+O3) 8 h per day during two months. The AOT40 values at the end of the experiment were 48, 910 and 12,895 ppb h(-1), respectively, for the three treatments. After 25 days of exposure (AOT40=3871 ppb h(-1)), interveinal red stippling appeared in plants in the NF+O3 chamber. In the NF chamber, symptoms were observed only after 60 days of exposure (AOT40=910 ppb h(-1)). After 60 days, injured leaves per plant corresponded to 19% in NF+O3 and 1% in the NF treatment; and the average leaf area injured was 7% within the NF+O3 and 0.2% within the NF treatment. The extent of leaf area injured (leaf injury index) was mostly explained by the accumulated exposure of ozone (r2=0.89; p<0.05).     

Anthocyanins and tannins in ozone-fumigated guava trees

Psidium guajava “Paluma”, a tropical tree species, is known to be an efficient ozone indicator in tropical countries. When exposed to ozone, this species displays a characteristic leaf injury identified by inter-veinal red stippling on adaxial leaf surfaces. Following 30 days of three ozone treatments consisting of carbon filtered air (CF – AOT40 = 17 ppb h), ambient non-filtered air (NF – AOT40 = 542 ppb h) and ambient non-filtered air + 40 ppb ozone (NF + O₃ – AOT40 = 7802 ppb h), the amounts of residual anthocyanins and tannins present in 10 P. guajava (“Paluma”) saplings were quantified. Higher amounts of anthocyanins were found in the NF + O₃ treatment (1.6%) when compared to the CF (0.97%) and NF (1.30%) (p < 0.05), and of total tannins in the NF + O₃ treatment (0.16%) compared to the CF (0.14%). Condensed tannins showed the same tendency as enhanced amounts. Regression analyses using amounts of tannins and anthocyanins, AOT40 and the leaf injury index (LII), showed a correlation between the leaf injury index and quantities of anthocyanins and total tannins. These results are in accordance with the association between the incidence of red-stippled leaves and ozone polluted environments.     

Peroxyacetyl nitrate (PAN) in the urban atmosphere

Peroxyacetyl nitrate (PAN) in air has been well known as the indicator of photochemical smog due to its frequent occurrences in Seoul metropolitan area. This study was implemented to assess the distribution characteristics of atmospheric PAN in association with relevant parameters measured concurrently. During a full year period in 2011, PAN was continuously measured at hourly intervals at two monitoring sites, Gwang Jin (GJ) and Gang Seo (GS) in the megacity of Seoul, South Korea. The annual mean concentrations of PAN during the study period were 0.64 ± 0.49 and 0.57 ± 0.46 ppb, respectively. The seasonal trends of PAN generally exhibited dual peaks in both early spring and fall, regardless of sites. Their diurnal trends were fairly comparable to each other. There was a slight time lag (e.g., 1 h) in the peak occurrence pattern between O₃ and PAN, as the latter trended to peak after the maximum UV irradiance period (16:00 (GJ) and 17:00 (GS)). The concentrations of PAN generally exhibited strong correlations with particulates. The results of this study suggest that PAN concentrations were affected sensitively by atmospheric stability, the wet deposition of NO₂, wind direction, and other factors.     

Technical Manual onSingle Retort Underfeed Stokers

Most of the recent work on the effects of cement-kiln dust has been confined to Germany and results differ considerably. There appears to be little doubt that naturally deposited dust from certain cement plants is responsible for leaf injury to deciduous and coniferous species and occasionally for death of the latter. Injury results from the combination of a relatively thick crust deposit and the toxicity of alkaline solutions formed when dusts are deposited in the presence of free moisture. The results of several hand-dusted field experiments, however, are not so conclusive; dusts are reported as either harmful, harmless, or even indirectly beneficial. In the present laboratory investigation, the comparison of CO₂ exchange in the leaf between dusted and nondusted leaves, as well as occurrence of obvious tissue damage, were used as the criteria of dust effects in short term experiments. The results demonstrated that the finer particles of certain cement-kiln dusts collected from electrostatic precipitators do interfere with CO₂ exchange and in some cases cause considerable leaf injury. The results further suggest that calcium content alone may not be the only indicator of whether a dust might be injurious, and that much more needs to be known about the effects of the interaction of chemical composition, particle size, and deposition rate.     

Simulation of effects of atmospheric ethylene on tree leaf shedding

This study made a preliminary assessment of the possibility that ethylene contained in polluted atmospheres affects leaf shedding of trees. The effect of ethylene dosage (ppb x h) on leaf shedding at various temperatures was approximated by using a polynomial regression. The effect of ethylene dosage on shedding of tree leaves with various sensitivities to this hydrocarbon was simulated in connection with the relationship between ethylene concentrations (10-100 ppb), dosage periods (0-50 days) and temperature (10-30 degrees C). The simulated results indicated the possibility that, for the tree group having high sensitivity, the rate of leaf shedding due to a dosage of ethylene with a concentration as low as 20 ppb, which is commonly observed in urban atmospheres, increased with temperature. On the other hand, the same concentration scarcely influenced leaf shedding in the low sensitivity group even at a temperature as high as 30 degrees C. The results for the real atmosphere determined at the Tokyo metropolitan center indicated the possibility that, for trees having high sensitivity, the rate of leaf shedding increased with rises in both monthly ethylene concentrations and air temperatures and reached a maximum of 90% in July. But in December when the concentration again reached the same value as in July while the mean monthly air temperature was 9.3 degrees C, the rate was only 10%.     

Foliar injury response of petunia and kidney bean to simultaneous and alternate exposures to ozone and pan

Petunia at about 6 weeks old and kidney bean at two growing stages (6–7 days old and 16–18 days old) were exposed separately to O₃, (0–0.40 ppm) and PAN (0–0.25 ppm) for 4 h and to the mixture for the same time. In addition, petunia was exposed to O, (0.10–0.40 ppm) and then PAN (0.010−0.040 ppm) for 4 h, respectively. Foliar injury of petunia and kidney bean in exposures to the mixtures of O₃ and PAN was significantly smaller than that induced by each oxidant, with the exception of PAN injury on young leaves of 16–18 day-old kidney bean. The percentage of foliar injury caused by either of the mixed pollutants decreased with an increase of the concentration of the other oxidant, and was found to approximate a logarithmic function of the combined pollutant concentrations expressed as O₃, minum PAN or vice versa. Alternate exposures caused no additive or synergistic injuries.