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.     

Chemistry of Atmospheric Oxidants

All of the important oxidants in polluted air are formed there by chemical reactions which occur among the primary pollutants. The most abundant of these oxidants is ozone which is formed in a cycle involving nitric oxide, nitrogen dioxide, atmospheric oxygen, and hydrocarbons. This ozone is best understood, not as a reaction product, but as an intermediate in steady-state concentration between formation and disappearance reactions. Hydrocarbons permit accumulation of ozone by reacting to scavenge the nitric oxide which would otherwise remove the ozone. The amount of ozone which can be formed in ambient polluted air is limited to about 1 ppm because these scavenging reactions become less effective when the nitric oxide concentration becomes very small. The peroxyacyl nitrates are a group of oxidants which result from reactions between oxides of nitrogen and organic pollutants. Olefinic and aromatic hydrocarbons make the largest contribution to PAN formation; saturates contribute little if any. The role of nitrogen dioxide and other oxidizing agents is also discussed.     

Further Effects of Temperature and Pressure on Photochemical Oxidant Production

A procedure is described for producing a sulfur dioxide (SO₂) contaminated atmosphere within a body plethysmograph, exposing man to this atmosphere while maintaining the SO₂ concentration at a given level, and measuring the concentration with less than a oneminute lag time. A syringe is used to introduce incremental volumes of SO₂ limiting the maximum SO₂ concentration in the chamber and assuring safety of the subject. A Titrilog SO₂ analyzer with its rapid response characteristics provides quick measurement of the SO₂ concentration. The body plethysmograph used in this manner serves simultaneously as a pulmonary function measuring device and as an exposure chamber.     

The Inhibition of Photochemical Smog

Additional inhibitors for the conversion of NO to NO₂ in C3H6—NO—0₂ irradiated mixtures have been tested at 25°C. These mixtures initially contained 16 mTorr C₃H₆, 8 mTorr NO, 0.012 mTorr NO₂, additive, and enough O₂ to bring the total pressure to 100 Torr. The NO₂ pressure was monitored photometrically. In the absence of additive, the NO₂ pressure first increases with irradiation time reaching a maximum conversion at about 15 minutes. As the irradiation time increases beyond 15 min, the NO₂ pressure drops. Before adding the inhibitors, runs were done with 10 Torr of CO added, and in these runs the conversion was speeded so that the maximum in NO₂ pressure occurred at 10 min. This enhancement in conversion rate is considered to be diagnostic for the presence of HO radicals. Next 10-min irradiations were done with various amounts of hexafluorobenzene (C₆F₆), nitrobenzene (C₆H₅NO₂), or naphtha lene (C₁₀H₈) added. The NO₂ pressure was reduced to one-half its value in the absence of inhibitor with 270 mTorr C₆F₆’, 220 mTorr C₆H₅N0₂, or 4 mTorr C₁₀Hg. The C₁₀H₈ is a very efficient inhibitor, but additions of up to 1 8.5 mTorr C₁₀H₈ did not reduce the N0₂ pressure to zero. Studies of the percent conversion of NO to NO₂ vs. irradiation time were done with either 4.2 mTorr C₁₀H₈ or 40 mTorr 2,6-di-ferf-butyl-4-methylphenol (Ph) added. In the former case the peak conversion was delayed from 15 to 22 min, while in the latter case no delay occurred. However, with the Ph added, there appeared to be some reduction in the maximum value of percent conversion.     

The Effect of Nucleating Particulates on Photochemical Aerosol Formation

The role of nucleating particulates in the formation of photochemical aerosols has been studied in a steady, laminar flow of ultrafiltered air containing NO₂ and octene-1 in the concentration range of (30 to 170 ppm) when subjected to intense irradiation under isothermal conditions. The particulates consisted of monodisperse polystyrene latex (d = 0.36 μ.) in concentrations similar to those in the atmosphere (6 × 10¹ to 3 × 10³ cm^–3); the irradiation intensity varied between (6 to 40 × 10³ lumen/liter) and the mean exposure duration between 30 and 180 sec. Samples of the flow prior to and after its photoactivation were withdrawn either by an Aerosol Spectrometer (AS) or by a Royco Aerosol Photometer (PH). While these indications refer thus to the same system, they differ, because the photometric data include all colloidal components in the airborne state, whereas the counts obtained from the AS deposits refer only to the nucleated latex particles. The following pattern becomes evident: The photochemical reaction yields fractional products (less than three percent) which have the tendency to agglomerate (or polymerize) due to their relatively low volatility—independent of the presence or absence of nucleating particulates. In their presence, this reaction becomes kinetically more probable and thus faster, hence the accumulant formation occurs preferably on the nuclei and causes their growth such that, e.g., a 10-fold higher nuclei concentration will produce under the same conditions 10 times the accumulant mass while autonucleation is suppressed. The growth process appears thus principally different from that of fog formation by H₂O-condensation, whereas for identical super saturation it is inversely proportional to the nuclear concentration. In the absence of nuclei autonucleation, i.e., self-agglomeration, occurs at a much lesser reaction rate and higher photon demand. The growth rate of the nuclei, when present, depends on the concentration of the oxidation catalyst (NO₂), its interaction with the nuclei surface is indicated. Under identical conditions the mass of nuclear accumulant is directly proportional to the concentration of the reactive hydrocarbon, while the growth rate depends on the light intensity and the exposure duration. The findings indicate that density and nature of particulate matter present in an air mass prior or during photo-activation are—aside from the chemical reactant levels—of major significance in aerosol formation.     

Relationship of Hydrocarbons to Oxidants in Ambient Atmospheres

The relation of ambient levels of hydrocarbons to the products of atmospheric photochemistry has proved to be an elusive problem. Models to account for the photochemical processes are available based on laboratory examination of simulated atmospheres. Likewise, dispersion models are available which, for nonreacting species, can predict air quality given knowledge of emission rates and meteorological variables. However, integration of the dispersion model with the photochemical model is as yet an unsolved problem. In this study an empirical approach was applied in which the only assumption made was that there exists a relationship between early morning average hydrocarbon concentrations and subsequent maximum hourly average oxidant concentrations. A direct examination of all available days in several cities shows that, at any given hydrocarbon level, there exists a limit on the amount of oxidant which can be generated. Specifically it shows that the average 6:00–9:00 A.M. concentration of 0.3 ppm C nonmethane hydrocarbon can be expected to produce a maximum hourly average oxidant concentration of up to 0.1 ppm.     

Effects of Land Use Data on Dry Deposition in a Regional Photochemical Model for Eastern Texas

ABSTRACT

Land use data are among the inputs used to determine dry deposition velocities for photochemical grid models such as the Comprehensive Air Quality Model with extensions (CAMx) that is currently used for attainment demonstrations and air quality planning by the state of Texas. The sensitivity of dry deposition and O₃ mixing ratios to land use classification was investigated by comparing predictions based on default U.S. Geological Survey (USGS) land use data to predictions based on recently compiled land use data that were collected to improve biogenic emissions estimates. Dry deposition of O₃ decreased throughout much of eastern Texas, especially in urban areas, with the new land use data. Predicted 1-hr averaged O₃ mixing ratios with the new land use data were as much as 11 ppbv greater and 6 ppbv less than predictions based on USGS land use data during the late afternoon. In addition, the area with peak O₃ mixing ratios in excess of 100 ppbv increased significantly in urban areas when deposition velocities were calculated based on the new land use data. Finally, more detailed data on land use within urban areas resulted in peak changes in O₃ mixing ratios of ~2 ppbv. These results indicate the importance of establishing accurate, internally consistent land use data for photochemical modeling in urban areas in Texas. They also indicate the need for field validation of deposition rates in areas experiencing changing land use patterns, such as during urban reforestation programs or residential and commercial development.     

Environmental Appraisal: And Oxides of Nitrogen Oxidants,Hydrocarbons

The relationships between criteria, standards, and control of air pollutants involve complex multidisciplinary interactions. Their over-all impact on the public health and welfare is directly related to the confidence level held by members of government, industry, and universities in the validity of the data upon which these criteria are based. The Environmental Appraisal section of the preliminary draft of the Air Quality Criteria Document “Photochemical Oxidant” prepared by the State of California, Department of Public Health, is reviewed. In general, it is a thoughtful and extensive effort to present the current status of information concerning the physical and chemical aspects of photochemical oxidant. Suggestions as to how it might be extended, revised, or updated are presented along with a brief discussion of two new research areas of possible interest, singlet molecular oxygen as a possible environmental oxidant, and the photochemistry of mixed lead halides in the atmosphere.     

表层土壤中有机污染物的光化学行为

本文首先简要介绍了光化学反应的基本原理。然后 ,重点介绍了研究表层土壤中有机污染物光化学行为的实验方法 ,影响光化学行为的因素及影响机理 ,光化学反应与吸附、迁移等的互相作用。最后阐述了这方面存在的问题 ,并且提出了一些建议     

Evaluation of an Ion Selective Electrode Monitor for Total Oxidants

The iodide ion selective electrode has potential use for continuous monitoring of total oxidants in ambient air. Total oxidants are measured coulometrically or colorimetrically after oxidation of neutral buffered Kl solution (0.6-1.2M) to free iodine. On the other hand, the iodide electrode can measure much more dilute solutions (<10^-4M). The iodide electrode measures the disappearance of iodide from the absorbing solution. The detector is made from an iodide electrode, reference electrode, an expanded scale pH meter, and millivolt recorder. The iodide electrode shows a constant Nernstian —59 mv change per decade over a dilute solution range although the absolute voltage shows a drift of 1 mv/day. A continuous iodide electrode air monitor was set up and investigated for ambient monitoring. Operational parameters as air and solution flow rates and electrode parameters as response time at different iodide concentrations were investigated. Statistical comparison was made with a Beekman colorimetric total oxidant monitor and a prototype REM chemiluminescent ozone monitor. The iodide electrode monitor was shown capable of continuously monitoring oxidants in the atmosphere being sensitive to changes in ambient concentrations.     

Photochemical behaviour of musk tibetene

BACKGROUND: Synthetic musk compounds are widely used as additives in personal care and household products. The photochemical degradation of musk tibetene in aqueous solutions or in acetonitrile/water mixtures under different conditions was studied in order to assess its environmental fate. METHODS: Musk tibetene dissolved (or suspended) in water and/or acetonitrile/water mixtures was irradiated at different times by UV-light and by solar light. The irradiation mixtures were analyzed by NMR and TLC. The photoproducts formed were identified by GC-MS and NMR data. RESULTS: The experimental results indicated that musk tibetene was photodegradable in water or acetonitrile/water mixtures with half-life reaction times close to 20 minutes. The irradiation mixtures were separated by chromatographic techniques yielding three photoproducts (3,3,5,6,7-pentamethyl-4-nitro-3H-indole, 3,3,5,6,7-pentamethyl-4-nitro-1H-indoline and 3,3,5,6,7-pentamethyl-4-nitro-3H-indolinone) identified by means of spectroscopic analysis. DISCUSSION: The numerical modelling of the photodegradation concentration-time profiles gave (8.13 +/- 0.15) x 10(-2) and (1.34 +/- 0.04) x 10(-2) mol/E for the overall primary quantum yield of direct photolysis for musk tibetene and the major intermediate (3,3,5,6,7-pentamethyl-4-nitro-3H-indolinone), respectively, in the wavelength range 305-366 nm. The half-life times of photodegradation of the both substances varied from 1-1.5 hours at 20 degrees N during the summer season to 6-10 hours for highest latitudes in winter. CONCLUSIONS: Under solar light, musk tibetene was photolabile in acetonitrile and acetonitrile/water 1/1, while it was slowly degraded when suspended in water. In all media, musk tibetene was photodegraded into three photoproducts. By using a kinetic model, the overall primary quantum yields of direct photolysis of musk tibetene and its main photoproduct, in the wavelength range 305-366 nm, were estimated, indicating that the photodegradation rate for musk tibetene is faster than the photolysis rate of the major by-product. RECOMMENDATIONS AND PERSPECTIVES: The results indicate that, in order to assess the environmental impact of musk tibetene on the aquatic ecosystem, great attention should be focused on the major photoproduct which is proved to be more persistent than the parent compound under light irradiation. The predicted half-life times of direct photolysis for both substances ranged from 1-1.5 hours at 20 degrees N during the summer season to about 6-10 hours for highest latitudes in winter, indicating that, from a photochemical point of view, the environmental persistence of these substances increases by increasing the latitudes and during the cold seasons, making more realistic an intake of these xenobiotic molecules into the food chain of aquatic living organisms. Tanabe reports in his Editorial (Tanabe 2005) that "It is necessary to have knowledge of the global picture of synthetic musk pathways. So, it is conceivable that now is the time to study the transport, persistency, distribution, bioaccumulation and toxic potential of this new environmental menace on a global scale, especially in developing countries". Therefore, the future environmental analysis and investigations on the eco-toxicity of nitro musk compounds should take into account not only the presence of the parent compounds but also their photochemical intermediates or end-by-products.     

The Fate of Aromatic Hydrocarbons in Photochemical Smog Systems: Toluene

The economic impact of various ozone concentrations on California agriculture is examined using an economic model of crop production that accounts for interdependence among crops. Such interdependence recognizes that net economic effects are determined not only by yield sensitivity to ozone but also by market conditions that affect relative crop prices and profitability. Changes in crop yields due to alternations in ambient ozone concentrations are used to drive the economic model. The predicted yield changes are derived from NCLAN data under a range of assumptions concerning functional form and yield effects. The results indicate that the economic effects of ozone are substantial for 13 included crops. The economic estimates display varying sensitivity to the functional form of the response relationship. The need for additional experimental data to more precisely define the relationship depends on the range of policy actions being considered.