The Effect of Water Vapor on Ozone Synthesis in the Photo-oxidation of Alpha-pinene

A study of the effect of water vapor on the photochemical system NO₂ + alphapinene + hv was conducted. A Hotpack Environmental Room was used as a constant temperature chamber, a bank of ultraviolet and fluorescent lamps as a source of simulated solar radiation, and a 150-liter FEP Teflon bag as a reaction vessel. Representative concentrations of 10 pphm NO₂ and 50 pphm alphapinene were used in a 3 × 2 × 2 factorial design where absolute humidities of 0.0000, 0.0090, 0.01 80 g H₂O/g dry air were varied.

Matheson zero air was passed through a clean air train and used as the diluent. Nitrogen dioxide was added to the reaction mixture by a permeation tube, and water and alpha-pinene by evaporation techniques.

Variables measured as a function of time over a 2-hour irradiation period were total oxidants (Mast Ozone Meter), condensation nuclei (General Electric Small Particle Detector), ozone (Regener Chemiluminescent Ozone Meter), nitrogen dioxide and nitric oxide (Technicon Autoanalyzer), and alpha-pinene (Perkin- Elmer Model 800 gas chromatograph).

Upon irradiation, systems containing nitrogen dioxide and alpha-pinene formed oxidants, ozone, condensation nuclei, and nitric oxide. Based on the differences between simultaneous oxidant and ozone measurements, the formation of peroxide- like compounds may be inferred. During the course of the irradiation, nitrogen dioxide and alpha-pinene were consumed. The concentration-time profiles of all variables were characteristic of those exhibited by typical photochemical smog systems.

An effect of water vapor on the systems studied was demonstrated. Increasing humidity decreased net mean/time oxidant and ozone production and net maximum condensation nuclei production. These effects were significant at a 0.05 confidence level. Effects of water on average mean/time NO₂, NO, and alphapinene concentrations were insignificant at this level. The oxidant to ozone ratio was found to decrease with increasing humidity.

The significant decreases in net oxidant and ozone production and NO₂ consumption with increasing water vapor concentration in systems of nitrogen dioxide alone, suggests that water manifests an effect on pertinent inorganic reactions, and the data also suggest additional water participation in the organic reactions.     

A Study of Sulfur Dioxide in Photochemical Smog I. Effect of SO2 and Water Vapor Concentration in the 1-Butene/NOx/SO2 System

There is an appreciable chemical interaction between SO₂ and photochemical smog which depends on the concentration of SO₂ and water vapor. The rate of decay of SO₂ concentration is greatly increased in the presence of photochemical smog. With 0.75 ppm SO₂, a light-scattering aerosol is produced in dry systems and systems at 22 and 55% relative humidity (RH). Aerosol is not observed until after the NO₂ peak has been reached and the NO concentration has fallen to a very low value. The formation of aerosol corresponds in time to the region of most rapid decrease in the SO₂ profile. In systems at 65% RH or with smaller amounts of SO₂, no light scattering is observed, but the percentage of SO₂ disappearing is greater. In relatively dry systems the presence of SO₂ results in a general slowing down of the photochemical smog reactions. In systems containing water vapor concentrations comparable to those found in the atmosphere, the inhibiting influence of SO₂ on the smog reaction is less pronounced. However, the maximum concentration of oxidant produced by the photochemical smog reactions is significantly lower when SO₂ is present.     

On the Relation Between the Indoor and Outdoor Concentrations of Nitrogen Oxides

Simultaneous measurements were made of the concentrations of NO, NO₂, and CO inside and outside of a building. The building is located in the Los Angeles area, which is heavily polluted by photochemical smog, and the experiments were conducted at a time of the year when the pollutants in question tend to be high. The results shows that there is a direct relationship between the inside and outside concentrations, and that the phase lag between the concentrations depends principally on the ratio of the building volume to the ventilation rate. Although the outside concentrations of the pollutants in question did not follow the same pattern every day, peak concentrations seemed to be related to “rush-hour” traffic. By reducing ventilation rates during these periods, it may be possible to reduce the concentration peaks inside of the building. The building involved in the current study was not located in the immediate vicinity of heavy traffic, and the indoor concentrations of NO, NO₂, and CO did not appear to be very severe when compared to those defined by present air quality standards. Finally, the results support the belief that NO and O₃ do not co-exist indoors except in very small quantities.     

Some Empirical Models for the Los Angeles Photochemical Smog Data

This paper presents (i) an empirico-mechanistic model which describes the dependence of CO, NO, NO₂, and O₃ on total hydrocarbons, traffic, wind speed, inversion base height, and solar radiation as well as the photochemical reactions associated with these pollutants; (ii) a detailed study of weather conditions when the instantaneous daily maximum O₃ exceeds the L.A. County alert level of 50 pphm; and (iii) regression models for the prediction of daily maximum O₃ values.     

The Inhibition of Photochemical Smog I. Inhibition by Phenol,Benzaldehyde, and Aniline

In urban atmospheres hydrocarbons promote the conversion of NO to NO₂ under the influence of sunlight, ultimately giving rise to photochemical smog. The conversion results from a long chain process with HO radicals as the chain carrier. If this chain could be interrupted by suitable radical traps, the formation of photochemical smog would be inhibited. In this paper we report the results of studies using phenol, benzaldehyde, and aniline as inhibitors. Mixtures containing 16 mTorr C₃H₆, 8 mTorr NO, ～85 Torr 0₂, and the addi tives were irradiated at 25°C. The NO₂ pressure was monitored photometrically. In the absence of additive, the NO2 pressure first increases with irradiation time reaching a maximum conversion corresponding to 70% of the NO at 1 2 minutes. As the radiation time is lengthened, the NO₂ pressure drops. With the additive present, the formation of NO₂ is delayed. The time to reach the maximum percent conversion of NO to N0₂ becomes 20, 22, 31, and 40 minutes respectively, for 13 mTorr C₆H₅OH, 2 mTorr C₆H₅CHO, 8 mTorr C₆H₅CHO, and 4.1 mTorr C₆H₅NH₂ added. The problems and possibilities of adding inhibitors to the atmosphere to control air pollution are discussed.     

An historical experiment: Los Angeles smog evolution observed by blimp

Observations of smog over the Los Angeles Basin (LAB) links high oxidant mixing ratios with poor visibility, sometimes <5 km. By the 1970s, investigators recognized that most of the aerosol affecting visibility was from gaseous oxidation products, sulfate, nitrate, and organic carbon. This led to the 1972–1973 Aerosol Characterization Experiment (ACHEX), which included observations at the ground and from aircraft. Part of ACHEX was the measurement of smog by blimp in a Lagrangian-like format. The experiment on September 6, 1973, demonstrated that a blimp could travel with the wind across the LAB, observing ozone (O₃) and precursors, and particles of different size ranges. These included condensation nuclei (CN) concentrations dominated by particles of ≤ 0.1 µm diameter and light scattering coefficient (b_sc) representing mainly particles of 0.1–2.0 µm diameter. The results indicated a pollutant variation similar to that measured at a fixed site. Ozone was produced in an air mass, reaching a maximum of ~400 ppb in the presence of nitrogen oxides (NO_x) and nonmethane hydrocarbons (NMHCs), then declined. Although the photochemistry was developing, b_sc grew with O₃ mixing ratio to a quasi-steady state at ~9–10 × 10^?4 m^?1, decreasing in value much later with decease in O₃. The light scattering coefficient was found to be positively associated with the O₃ mixing ratio, whereas CN concentrations were negatively proportional to O₃ mixing ratio. The blimp experiment was supported with aircraft vertical profiles and ground-level observations from a mobile laboratory. The blimp flight obtained combined gas and particle changes aloft that could not be obtained by ground or fixed-wing aircraft measurements alone. The experiment was partially successful in achieving a true Lagrangian characterization of smog chemistry in a constrained or defined “open” air mass.

Implications: The Los Angeles experiment demonstrated the use of a blimp as a platform for measurement of air pollution traveling with an air mass across an urban area. The method added unique data showing the relationship between photochemical smog chemistry and aerosol dynamics in smog. The method offers an alternative to reliance on smog chamber and modeling observations to designing air quality management strategies for reactive pollutants.     

Chemistry and Meteorology in an Air Pollution Episode

Strikingly sharp vertical boundaries occasionally develop between marine air polluted with photochemical smog and clean, dry air. Records of a particular incident which occurred in Riverside, Calif., shed some light on the role of wind and temperature structure in creating this unusual condition.     

A chamber study of photochemical smog in Melbourne,Australia—present and future

The present paper concludes a comprehensive program designed firstly to locate the source areas of emission responsible for the photochemical smog which impacts the central Melbourne urban area, secondly to determine the hydrocarbon and NO_x composition of these sources and finally to demonstrate by smog chamber simulations what benefit would be derived from a reduction in the emissions from the offending sources.The conclusions reached are that a reduction in NO_x emissions would lead to increased ozone levels in Melbourne but even a small reduction in hydrocarbon emissions would be beneficial. The implementation of Australia Design Rule 37 should, by restricting hydrocarbon emissions to 50% of the current 1985 level, reduce the photochemical ozone over the central metropolitan area to well below the acceptable level.In the course of this work it has been possible to validate the chamber technique by showing that the photochemical behaviour of a well-documented air parcel can be reproduced in a smog chamber operated under the same conditions of temperature, radiation, dilution and pollutant input as was experienced by the outdoor air parcel.     

Summer Ozone Concentrations in Southern Ontario in Relation to Photochemical Aspects and Vegetation Damage

In the summers of 1960 and 1961, groups from the Canada Department of Agriculture, the Meteorological Service of Canada, and the Canada Department of National Health and Welfare conducted a joint study in a tobacco-growing area along the north shore of Lake Erie. The purpose of the study was to determine the causal agent for weather fleck damage to tobacco crops. A number of air pollutants were monitored and the results correlated with extensive observations of meteorological phenomena and effects on rate of growth and fleck damage to leaves of tobacco plants in experimental plots. Ozone concentrations followed a diurnal cycle, rising a few hours after sunrise, peaking in early afternoon at about 5 pphm, and dropping to a minimum of less than 1 pphm during the night. Other measurements indicated the presence of NO₂ in the order of 1 pphm, aldehydes about 0.2 pphm or lower, and negligible concentrations of SO₂. Cracking of stretched rubber strips followed the ozone values although, in general, the cracking index was greater than could be attributed to ozone (by oxidized KI) alone. The maximum ozone value recorded during the two growing seasons was IS pphm. A dosage of 20 pphm-hr was found sufficient to cause weather fleck or ozone damage to susceptible tobacco leaves. In addition meteorological data could be used to predict weather fleck attacks one to four days in advance.     

Los Angeles Gasoline Modification: Its Potential as an Air Pollution Control Measure

A joint project of government and industry people who studied the possible effect upon air pollution in Los Angeles of variations in the composition of gasoline sold in Los Angeles is discussed.

No experimental automotive test work was undertaken in this project. However, prototype fuel blends were made and analyzed in order to simulate the effects certain changes would have upon photochemical smog formation.

It is apparent from the results of this study that the potential of reducing smog in Los ngeles by fuel modifications is quite small, even in the year of maximum effect. This potential decreases to a negligible level due to the effectiveness of mechanical control of evaporative losses required in California starting with the 1970 model cars.     

Nitrogen Dioxide and Nitric Oxide in Non-Urban Air

Measurement of NO₂ and NO has been carried out in Piedmont, N. C. and in the southern Appalachian Mountains. Average values for the Piedmont were: continuous NO₂ measured 30 ft above surface, 0.76 pphm (14.3 μg/m³), 1 20 ft, 0.61 pphm (11.5 μg/m³); simultaneous values (also Piedmont) (2-hr discrete samples) taken at an earlier time at 4 ft, NO₂, 0.56 pphm (10.6 μg/m³), NO, 0.19 pphm (2.34 μg/m³). The mountain top values (5120 ft, 1573 m) were: NO₂, 0.46 pphm (6.4 μg/m³), NO, 0.26 pphm (2.72 μg/m³). The results of this study furnish further proof that tropospheric NO and NO₂ are produced at the surface of the earth. Data obtained are consistent with the belief that a major sink for NO_x is reaction with O3 and ultimate conversion to nitrate.

Ozone values frequently increased and NO_x values decreased ahead of cold fronts, probably as a result of deep vertical mixing. Also, in small scale turbulence the changes in NO_x values and in the O₃ values tended to be “out of phase,” i.e., as O₃ concentration increased, NO_x concentration decreased and vice versa. Values of NO_x from Green Knob, N. C. (mountain top) also tended to be higher at times when O₃ values were lowest.

The NO₂ hourly average values in Piedmont, N. C, demonstrated a diurnal cycle reminiscent of diurnal urban changes. An early morning peak was followed by a minimum in mid-afternoon. Next, the values rose to a broad evening peak and then decreased slowly during the night. Reported urban concentrations are usually about ten times those found in Piedmont, N. C.     

Comparisons of ambient air particulates concentrations (TSP,PM2.5) and dry depositions during smog and non-smog periods at Luliao,Shalu District sampling site

The concentrations of ambient total suspended particulates (TSP) and PM_2.5, and the dry depositions at a sample site at Luliao Junior High School (Luliao) in central Taiwan were measured during smog and non-smog days between December 2017 and July 2018. The results are compared to those obtained during non-smog periods in the years 2015–2017. The mean TSP and PM_2.5 concentrations and dry deposition flux were 72.41?±?26.40, 41.88?±?23.51?μg/m³, and 797.57?±?731.46?μg/m² min, respectively, on the smog days. The mean TSP and PM_2.5 concentrations and dry deposition flux on the non-smog days were 56.39?±?18.08, 34.81?±?12.59?μg/m³ and 468.93?±?600.57?μg/m² min, respectively. The mean TSP concentration in the smog period was 28% greater than that in the non-smog period, and the mean PM_2.5 concentration was 20% higher. The mean dry deposition flux in the smog period was 70% higher than that in the non-smog period at Luliao. The PM_2.5 concentrations exceeded the standards set by the Taiwan EPA (35?μg/m³ daily, and 15?μg/m³ annually). Therefore, the TSP and PM_2.5 concentrations and dry deposition must be reduced in central Taiwan on smog days. In addition, atmospheric TSP and PM_2.5 concentrations at various sampling sites were compared, and those herein were not higher than those measured in other countries. Finally, apart from the local traffic emissions, during smog periods, the other pollution source originated from the transportation process of traffic pollutants emitted in the northwest side of Taiwan.     

Air pollution in cities

Air quality in cities is the result of a complex interaction between natural and anthropogenic environmental conditions. Air pollution in cities is a serious environmental problem – especially in the developing countries. The air pollution path of the urban atmosphere consists of emission and transmission of air pollutants resulting in the ambient air pollution. Each part of the path is influenced by different factors. Emissions from motor traffic are a very important source group throughout the world. During transmission, air pollutants are dispersed, diluted and subjected to photochemical reactions. Ambient air pollution shows temporal and spatial variability. As an example of the temporal variability of urban air pollutants caused by motor traffic, typical average annual, weekly and diurnal cycles of NO, NO₂, O₃ and O_x are presented for an official urban air-quality station in Stuttgart, southern Germany. They are supplemented by weekly and diurnal cycles of selected percentile values of NO, NO₂, and O₃. Time series of these air pollutants give information on their trends. Results are discussed with regard to air pollution conditions in other cities. Possibilities for the assessment of air pollution in cities are shown. In addition, a qualitative overview of the air quality of the world's megacities is given.     

Modeling the formation,decay, and partitioning of semivolatile nitro-polycyclic aromatic hydrocarbons (nitronaphthalenes) in the atmosphere

A nitronaphthalene kinetics mechanism has been implemented and added to the photochemical smog mechanism, Carbon Bond-4. This mechanism was used to simulate the formation, decay, and partitioning of 1- and 2-nitronaphthalene and compare it to outdoor smog chamber data. The results suggest that these types of mechanisms can be used to model nitronaphthalene formation and decay in regional airmasses. The partitioning experiments were conducted at night. The sampling system consisted of two Teflon impregnated glass fiber filters followed by a gas-phase denuder. Evidence is provided that partitioning equilibrium is maintained even when the gas-phase components are decaying rapidly under sunlight. The photolysis rate constants were determined relative to k_NO2 to be 0.07×k_NO2 and 0.005×k_NO2 for 1- and 2-nitronaphthalene, respectively. Our results confirm that gas-phase photolysis is the major degradation pathway for 1-nitronaphthalene, whereas for 2-nitronaphthalene other pathways may also be important. The photochemical formation of nitronaphthalenes was studied using a mixture of naphthalene, propylene, NO_x, and diesel particles. 2-nitronaphthalene was observed to build up to higher levels than 1-nitronaphthalene, as the photodegradation of the latter was faster. Additionally, as a part of this study 1-nitronaphthalene has been identified and quantified in diesel exhaust.     

An Evaluation of the Fuel Factor Through Direct Measurement of Photochemical Reactivity of Emissions

Findings in research at the Bureau of Mines Bartlesville Petroleum Research Center show that photochemical reactivities of vehicular emissions are reliably measured in laboratory experiments in which smog manifestations are observed directly. Results of the direct smog-chamber measurements reveal that the photochemical behavior of emissions may differ significantly from the behavior that is predicted from the exhaust composition using reactivity scales. The concept of direct measurement of reactivity was applied to determine differences in characteristics of emissions from 20 passenger vehicles, each tested using 10 different fuels. The primary objective of the fuel study was to assess the over-all effect on vehicle emissions of fuel modifications designed to reduce the photochemical pollution associated with automotive evaporative losses. A similar, brief, comparative study of leaded and nonleaded fuels was also made. Reducing volatility was found to reduce the over-all smog potential of vehicle emissions but involved some penalty by way of increased exhaust emissions. Replacing light olefin with the corresponding paraffin also reduced over-all smog potential and in this case exhaust reactivity was not affected. In general greater smog potential was found to be associated with prototype nonleaded fuels than with leaded fuels typical of products currently marketed.     

Evaluation of the mutagenic effect of N,N-diethylhydroxylamine in Salmonella typhimurium TA 100

A recent approach suggested to suppress photosmog formation has been the addition of small quantities of N,N-diethylhydroxylamine (DEHA) to the polluted air. Thus knowledge of possible mutagenic properties of the compound became important. DEHA was investigated using the Ames Salmonella/microsome mutagenicity test. Toxicity as well as a mutagenic effect were observed at concentrations much exceeding those proposed for practical application.It is well known that photochemical smog arises via the long chain free radical oxidation of NO to NO₂ in hydrocarbon containing atmospheres¹. Thus one recent approach suggested for alleviating smog formation has been the addition of small quantities of free radical scavengers (“photosmog inhibitors”) locally to the polluted air. Of the substances tested, mainly aromatic compounds and ammonia derivatives^2,3, N,N-diethylhydroxylamine (DEHA) has proven sufficiently active to be selected for field trials⁴. In this context the effect of DEHA exposure on living organisms is obviously of interest. Massie and Williams⁵ have recently reported an insignificant change in life-span of fruit flies after exposure to DEHA at concentrations of up to 89 ppm. In judging the safety of environmental chemicals, however, mutagenic testing is of great importance. We therefore under took the investigations described below employing the Salmonella/microsome test.     

Mathematical Modeling of Photochemical Smog Using the PICK Method

A new method for solving the turbulent atmospheric diffusion equation has been developed based on Lagrangian mass points, or particles moving through an Eulerian grid. The method is one of a family of Particle-/n-Cell techniques but is a unique extension to incorporate the effects of turbulent diffusion based on K-theory; thus the acronym PICK.

In the three-dimensional computer-aided model, NEXUS (Numerical EXamination of Urban Smog), this method has been applied to simulation of carbon monoxide (CO) in Los Angeles. For CO the NEXUS simulation was within 20% of observed day-averaged concentrations at 12 stations and the hour-averages were also in good agreement. This model was extended to include the effects of photochemical smog in Los Angeles. The results of the photochemical simulation were also qualitatively correct due to rapid NO to NO₂ conversion in the simulation.     

Glass Fibers and Their Use as Filter Media

Typical air quality effect levels of photochemical oxidants on specific plant substrates are illustrated. These include ambient oxidant exposure data measured as “total oxidant” as well as laboratory exposures to individual pure oxidants, ozone, or PAN compounds, since these oxidants are identified in photochemical smog. New terms, “PaNs” and “PAN-type” oxidant, have been proffered for purposes of clarification of the terminology. PAN-type oxidant more precisely defines the phytotoxicant complex causing silvering or bronzing of the lower leaf surfaces in lieu of the older term “oxidant.” Due to the recognition of several oxidizing phytotoxicants in recent years, it is recommended that the term oxidant be reserved for use as a generic term. A tabular classification of the oxidizing phytotoxicants found in community photochemical smog and the specific syndromes produced is provided.     

Ultrastructural Effects Of Air Pollution on Lung Cells

The lungs of exposed mice taken during 2- to 3-hour heavy smog periods (over 0.4 ppm total oxidants) showed various degrees of cytoplasmic damage in the alveolar epithelial cells. The extent of damage was markedly age-dependent. Alveolar wall cells taken during heavy smog from 5-month-old animals contained slightly more lamellar inclusion bodies than corresponding animals kept in clean air. The cytoplasm of alveolar cells of 9-month-old animals sacrificed during heavy smog was severely disorganized; however, animals of this age showed a marked recovery 14 hours following the smog peak. In a group of older mice (21 months), similar cytoplasmic damage was obvious, and those sacrificed 24 hours after the heavy smog peak showed even more cellular disruption, suggesting irreversible damage in the older animals. The effect of synthetic photochemical smog showed a pattern of ultrastructural alterations similar to that of the heavy natural smog. Some permanent changes occurred in alveolar cells of 15-month-old mice. Partial recovery of lining cells took place, but few wall cells and phagocytes remained. If older lung tissue has relatively fewer wall cells as is indicated, recovery is decreased to the point of permanent damage. Coupled with extensive disruption of lining membranes, exposures of this nature may well cause the death of older animals.     

Modeling alkene chemistry using condensed mechanisms for conditions relevant to southeast Texas,USA

Alkenes are important in photochemical smog formation in southeast Texas due to their high emissions, especially from industrial sources in and around Houston, and their high reactivities. Therefore, properly characterizing the chemistry of alkenes in condensed mechanisms used in regional photochemical models is important in understanding the formation of ozone and other photochemical air pollutants in Houston. The performance of three versions of the SAPRC condensed chemical mechanism family, for predicting ozone and radical formation, was compared. Simulations were compared to environmental chamber data and ambient data. The analyses showed that separately modeling individual alkenes reactions (especially propene for southeast Texas) has the potential to lead to more accurate simulations of alkene chemistry. Caution must be exercised in un-lumping, however. Testing with different formulations of the 1-butene + O₃ reaction demonstrated the complexity and interconnectedness in choices of stoichiometric parameters for un-lumped species and the extent to which lumped mechanisms are un-lumped.