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Fig. 4. The few substances shown in this table as being overly abundant in city air do not nearly exhaust the list. Absent are hydrocarbons by the hundreds—some of them potent carcinogens in laboratory animals and the highly toxic gas nitrogen dioride. Since these two react with each other under the stimulus of solar ultraviolet radiation--to produce photochemical smog with its characteristic haze, eye irritation, and damage to sensitive plante-it is perhaps fortunate that pollutants help cut down on solar ultraviolet reaching street levels in the city. Of course some air bacteria that might be killed by such uv are not, but one must be grateful for small favors when living in the urbs.
standable differences in outlook between industrial and public health people over which substances and which industryg'-emissions should be controlled. Many industrial people, including the most enlightened ones, remain somewhat loathe to pursue very much controlorientated research in the absence of definitive legal standards based on equally definitive criteria. Indeed, the automobile industry claims it wants such criteria precisely so it will know where it stands over the longer haul. It points to its experiences of recent years in California, the State that has led the country--perhaps the world as well-in pollution-control activities. California has more cars and a more poorly ventilated climate, in the Los Angeles area anyway, than any State in the Union. It also is richly endowed with sunshine. So it's not surprising that it leads the country in its concern about the auto component of its air pollution problem.
Auto exhausts emit two main contaminants : hydrocarbons and nitrogen oxides. The hydrocarbons come mostly from fuel that is not completely oxidized to carbon dioxide and water during engine operating cycles. The hydrocarbons are
diverse in kind-compounds originally in the fuel as well as new compounds that are formed during the hightemperature combustion process. Nobody has identified all of the compounds, but there were about 200 of them at last count. Nitrogen oxides, particularly nitric oxide (NO) with lesser amounts of NO,, result from the hightemperature dissociation of molecular nitrogen and oxygen from the intake air used to burn the fuel. The liberated atomic nitrogen and oxygen then combine to yield the oxides. These reactions are reversible at high temperatures, but they are prevented from reversing--the two oxides are literally “frozen in"--as combustion temperatures drop rapidly from peak values during expansion of the gases in both auto engine cylinders and powerstation exhaust stacks.
Of these two groups of contaminants California has so far established emission standards only for the hydrocarbons, chiefly because it was originally thought that the nitrogen oxides in auto (and other) exhausts would be far more difficult, and maybe unwise to eliminate. It was also felt originally that reducing the concentration of either one of the starting reactants would help reduce the buildup of troublesome final photochemical reaction products in the air.
Over the years, as California re-inventoried the dimensions of its pollution problems in finer detail, changes were made in automobile and other emission limits. The average uncontrolled automobile exhaust emits about 700 ppm hydrocarbong. Current California standards, set by the State Department of Health and approved by the legislature, limit this to 275 ppm and include an additional restriction
atomic powered instead of fossil-fuel-powered generating stations, or, farther in the future perhaps, cars operated by batteries or fuelcells instead of internal combustion engines, or electrified mass transportation. The art of pollution-control is not so much primitive in technical means as deficient in social ones. Whether anybody has to do anything about the pollutants that their products or processes emit-and how well they must do it-depends in part on progress made farther back along the "ideal" pollution control chain. Here the first step-setting air-quality criteria--is the most crucial. It is also the most complex,
Though all the needed data are not in, most people would agree, I think, with Vernon Mackenzie, head of PHS' Division of Air Pollution. when he says that "we must ... get on with the job of developing air-quality criteria and standards against a background of technical and scientific knowledge which is not now and probably never will be perfect." Engineers can recognize the validity of this approach; as professionals they live with it. There's a worm or two in the apple
Nevertheless, in view of large gaps in existing knowledge about the chemistry of normal and polluted atmospheres, there are under
on carbon monoxide of 1.5% (the average exhaust emits perhaps 3%), for reason of its own toxicity and its rising concentration in Los Angeles air, not because it contributes to photochemical smog. By 1970 the state will reduce these limits still further, to 180 ppm and 1 respectively. But even now, for reasons that we will discuss shortly, the Los Angeles County Air Pollution Control District-the trail-blazing agency in photochemical pollution control—would like to see the hydrocarbon limit reduced to below 100 ppm.
Such differences in opinion on the part of different control agencies is of course not frivolous in intent. It reflects uncertainty about precisely what should be controlled, and by how much. But at each such turn in the road to inevitable controls, a good deal of prior research on control techniques gets bypassed. And at the spectre of a patchwork of differing, locally determined control limits a national industry, like the auto industry in particular, gets understandably upset. To more clearly understand the basis for some of these difficulties we need a closer look at the nature of the smog which now afflicts all urban regions that are highly populated with automobile traffic. Sun-stewed auto exhaustsmog
Photochemical smog's chief immediate and obvious symptoms are eye irritation, damage to sensitive plants (as far as 100 miles from urban centers), accelerated cracking of rubber, and decreased visibility due to the formation of a haze of solid and liquid particles which are collectively described as aerosols. The first three symptoms are caused by the products of a complex of reactions that start, as we said, with hydrocarbons and oxides of nitrogen. In the course of the reactions some highly reactive intermediates and ozone are formed. These help polymerize the organic compounds in the mixture, according to Prof. A. J. Haagen-Smit of CalTech who pioneered work in this field, and lead to the formation of additional, non-volatile, oxidation and polymerization products which add to haze and eye irritants from other sources of pollution.
This kind of pollution is characterized by the same extreme dilution of reactive constituents and intermediate and final reaction products that characterize all air pollution. An ozone concentration of 0.3 ppm for instance is 10 times its normal background concentrations at ground levels. Haagen-Smit points out that this extreme dilution is one reason why it takes many years to unravel even relatively simple atmospheric reactions such as the photodecomposition of acetone. In ordinary laboratory work, "slow" and "fast" reactions are characterized against a backdrop of reactant concentrations that average about 10%. But in atmospheric reactions concentrations are only on the order of one-millionth as much. Under these conditions reactions which
so, Concentration (age)
Fig. 5. High wintertime concentrations of so, in air over (British) cities and surrounding regions come from burning of sulfur-bearing coals and add to ordinary cardio-respiratory hazards of winter weather, especially for the elderly. The map makes clear that pollution is not just a downtown problem; nor is the so, problem erclusively a British one. Abatement efforts center on switching to low-sulfur fuels and eliminating So, from flue gases.
would proceed in thousandths of a second at ordinary laboratory concentrations take an hour in the atmosphere.
This is important: It is essentially what permits the highly potent ozone to survive attack by reducing agents such as So, in the atmospheric mixture. Ozone thus can go on to participate in reactions at several stages in the photochemical chain. The immense slowdown in reaction rates also gives ozone and various, highly reactive, free radicals that are formed a far better chance to survive long enough to play significant roles, not only in the over-all reactions but in some of the observed symptoms as well.
The still far from completely elucidated chain of daily reactions leading to smog is set in motion by the photochemical dissociation of nitrogen dioxide. It is a yellowbrown gas that most effectively absorbs pho
CO2 Concentration (ppm)
% Increase Since 1900
1900 1920 1940 1960
Year Fig. 6. Accelerating use of fossil fuels may result in 50% rise in amount of co, in the air by year 2000. If not absorbed by sea and plants this could raise temperatures several degrees by enkanced "greenhouse" effect, enough perhaps to melt glaciers and flood coastal cities.
THE SUDDEN PEAKING OF POLLUTANTS
radicals. And these, in turn, can react with oxygen to form more ozone, with NO to form larger quantities of chain-initiating NO., and with NO., to produce short-lived but plant damaging peracylnitrates (usually abbrevj. ated to PAN) and an abundance of more stable oxidation products such as eye-irritating formaldehyde.
Bewildered? Let's go over it again with reference to Fig. 8. The pivotal group of oxidizing substances consists of atomic oxygen (from dissociation of NO.), excited molecular oxygen (from solar irradiation of the atmosphere's abundant molecular oxygen), peroxyl radicals (from the action of other oxidants on hydrocarbons), and ozone (formed as a by. product in several of the photochemical reactions). During the daylight hours all of the oxidants contrive to react with the original starting materials—hydrocarbons (particularly unsaturated, olefinic ones and some aromatics) and nitrogen oxides—as well as with their reaction products. Thus at any particular time, the air is filled (relatively speaking-remember the troublesome concentrations are down at or below the part per million level) with a very complex mixture of intermediate oxidation and reaction products. Unquiet controversy in California
A vast amount of experimental and theoretical photochemistry remains to be done at the low concentrations and low temperatures which characterize polluted atmospheres before we completely understand these processes. In the laboratory (Fig. 9, 10) symptoms of photochemical smog can be produced by ir. radiating with mock sunlight suitably low concentrations of hydrocarbons in the presence of oxides of nitrogen. But considerable controversy exists among both atmospheric chemists and simulators of smog about the precise course and time constants of each of the innumerable reactions occurring in polluted atmospheres. Not all such disputes are academic; indeed one such controversy is particularly instructive. It illustrates in a simple way the difficulty of understanding what our pollution problems really are and casts a long shadow over approaches to controlling photochemical pollution.
Although nitrogen oxides and hydrocarbons are the essential starting ingredients, only hydrocarbons are now being controlled in California, as was mentioned. This also is the control approach called for in a recent bill proposed to Congress and aimed specifically at the motor vehicle pollution problem. It should work; according to the tenets of the familiar chemical law of mass action this should inhibit formation of even the minute concentrations of final photochemical reaction products. Indeed, the consensus among pollution experts in Washington, Detroit and California is that by reducing hydrocarbons enough now,
Oddant 0.1 0.2 0.3
tons in the blue and near ultraviolet. This dissociation produces nitric oxide and atomic oxygen NO, + hv — NO + 0. The atomic oxygen thus formed combines with atmospheric oxygen molecules to form ozone (03).
Other photochemical reactions that contribute to the stew form excited oxygen molecules. These and ozone, perhaps aided by atomic O present in some dynamic equilibrium concentration, attack organic materials, probably by removing hydrogen atoms from the hydrocarbons. This oxidizing assault forms reactive intermediate substances such as alkyl and acyl radicals. These radicals can unite with oxygen to form still more reactive peroxyl
most of the ill effects associated with high oxidant levels that characterize photochemical smog can be eliminated, without any need for controls on nitrogen oxides for the time being. Others, Haagen-Smit among them, want both ingredients controlled. Still others feel most uneasy about nitrogen oxides. They feel the consensus on the hydrocarbon control approach may be too naive, in that it equates the eye irritation symptoms exclusively with the end products of irradiation. These products reach peak concentrations in experimental chambers after some 442 hours of irradiation. But Walter Hamming and colleagues of the Los Angeles County Air Pollution Control District have shown that there is an earlier peak of eye irritation observed in many irradiation chamber studies. It is equal in severity to the later one but it occurs only about 14 hours after irradiation has begun, and not only in simulation studies but in downtown Los Angeles after sunrise as well. This is long before oxidants such as ozone or PAN have reached any appreciable concentration. Indeed, this early irritation peak seems to coincide most closely with maximum NO.. Thus, Hamming and his coworkers feel that controlling nitrogen oxide emissions equals or exceeds hydrocarbon control in importance in alleviating Los Angeles' most obvious problem.
There's another interesting angle to all this. Hamming points out that the severity of eye irritation produced seems to relate to the intensity of sunlight involved. It turns out that for conditions in Los Angeles region partial control of hydrocarbons alone could possibly lead to more severe and extended periods of eye irritation. Since the early peaking NO, wouldn't have enough hydrocarbons available to be used up in zipping on down the photochemical reaction pike it might hang around longer and reach higher daily averages. In any case, Hamming feels that reducing nitric oxide emissions in any degree can only reduce the severity of eye irritations whereas hydrocarbons would have to be limited much more drastically than is currently envisioned to achieve equally effective relief.
This tempest over tearing eyes in Los Angeles may have deadlier ramifications. The need for controlling NO and NO:
Obviously, differences in opinion needed control measures depend on the symptoms that concern one. The control waters have all too often been muddied by imprecise definitions here. Precise definitions are needed, and soon, before going too far with control attempts limited to single, more easily controlled components of complex reaction mixtures. NO. itself for instance is acutely toxic at about 100 ppm. The limiting concentration that industrial hygienists allow for it and other oxides of nitrogen in workroom air is 5
Free Radicals + NO2 -Peroxyacylnitrates (PAN),
Rubber Cracking Fig. 8. Starting substances for smog are nitrogen oxides and hydrocarbons. The critical first step leading to group of oxidizing substances is photodissociation of Noz; this yields atomic o that joins molecular oxygen to produce ozone. Oxidants attack hydrocarbons and produce reactive free radicals of several kinds which are also capable of attacking hydrocarbons and participating in other reactions as indicated. As discussed in story, eye irritation may relate more to NO, content than to final reaction products shown.
GM Sator UK
Fig. 9. Smog simulation chamber used by General Motors uses banks of fluorescent lamps enclosed within chamber to simulate sunlight. Spectral matching curves are sketched in the margin. Irradiation is carried out on dilute mixtures of hydrocarbons and nitrogen oxides.
of the British Medical Research Council Group on air pollution) had in mind, several years ago, when he said regarding British urban air pollution: "We have no more right to expect an easy solution than to overlook a simple answer. The field is bedevilled by paradox, not the least striking of which is the persistence with which we apply exquisitely fine techniques to crude problems and at the same time expect delicate mechanisms to yield to the hammer blows of our clumsier methods."
The British are plagued by pollution problems characterized more by SO.and its involved atmospheric permutations to SO, and sulfuric acid than by the automotive kind of smog. But this is changing, of course, as autos and traffic congestion increase, just as the SO.:-complex never was exclusively a British problem.
Sulfur dioxide in the air comes mostly from combustion of sulfur-containing fuels-coal and low-grade or residual fuel oils are the chief offenders. Natural gas and light petroleum fractions like kerosenes and gasolines are relatively low in sulfur or can be made so with little difficulty. Some SO, also comes from the smelting of sulfide ores. The ash constituents invariably present in the air help to catalytically oxidize SO., to SO,,, and hydration of SO, yields the sulfuric acid which is responsible for the blue color typical of So,-laden exhaust plumes.
The more difficult and critical transformation of So, to SO, is probably accomplished photochemically by near ultraviolet radiation; this mechanism may be most effective in the presence of particles of manganese and iron salts or oxides, under the moisture-rich conditions available in most stack gases and during humid weather conditions more generally. No doubt the strongly oxidizing atmosphere created in typical photochemical (Los Angeles) smog also contributes significantly to this otherwise slow oxidation step. Both kinds of smog are invariably present to greater or lesser degree in urban atmospheres and their deleterious effects, as to some extent their photochemical histories, are intricately entangled, but distinguishable.
The U.S. Clean Air Act specifically recognized the sulfur problem too, and it directed Health, Education and Welfare to conduct a major R&D effort aimed at developing cheaper and better techniques for removing sulfur from the offending fuels. Much additional work is being done on an alternative potential solution-removing the sulfur compounds from exhaust gases before emitting them to the atmosphere. Several lines of development look promising here. Some involve adsorption of So, on activated carbon char or reacting it with alkalized alumina. Others approach the problem as the atmosphere itself does, by catalytically oxidizing the So, to SO, and con
ppm; this limit is for 5-day-a-week, 8-hr-aday exposures of healthy adult workers. A value of twice this amount or 10 ppm observed in a single measurement in ambient air in Los Angeles would result in a so-called "third alert” in which all-out community protection measures would be authorized. Most of the time the LA concentration of NO and NO:which are usually measured together since there appears to be no control purpose to be served in distinguishing between them in view of the rapid conversion of NO into NO.:--stays below about 1 ppm. One thing that may help keep NO and NO., well below more potentially dangerous levels most of the time is that during the daylight hours, they are continually used up in maintaining the series of equilibrium reactions with ultraviolet light and hydrocarbons. But some knowledgeable scientists, such as Philip Leighton of Stanford University and Albert Bush of UCLA, have warned that reducing hydrocarbons alone especially to drastically low levels such as 100 ppm or less—may in fact raise the total of nitrogen oxides in the air over the long term, eventually perhaps to more dangerous levels. Hamming and most others discount this possibility, however.
Such fundamental uncertainties as these must have been what Dr. P. J. Lawther (then