Fifty Years of Clearing the Skies

A Milestone in Environmental Science
Ringed by mountains and capped by a temperature inversion that traps bad air, Los Angeles has had bouts of smog since the turn of the 20th century. An outbreak in 1903 rendered the skies so dark that many people mistook it for a solar eclipse. Angelenos might now be living in a state of perpetual midnight—assuming we could live here at all—were it not for the work of Caltech Professor of Bio-organic Chemistry Arie Jan Haagen-Smit. How he did it is told here largely in his own words, excerpted from Caltech's Engineering & Science magazine between 1950 and 1962. (See "Related Links" for the original articles.)
Old timers, which in California means people who have lived here some 25 years, will remember the invigorating atmosphere of Los Angeles, the wonderful view of the mountains, and the towns surrounded by orange groves. Although there were some badly polluted industrial areas, it was possible to ignore them and live in more pleasant locations, especially the valleys . . . Just 20 years ago, the community was disagreeably surprised when the atmosphere was filled with a foreign substance that produced a strong irritation of the eyes. Fortunately, this was a passing interlude which ended with the closing up of a wartime synthetic rubber plant. (November 1962)
Alas, the "interlude" was an illusion. In the years following World War II, visibility often fell to a few blocks. The watery-eyed citizenry established the Los Angeles County Air Pollution Control District (LACAPCD) in 1947, the first such body in the nation. The obvious culprits—smoke-belching power plants, oil refineries, steel mills, and the like—were quickly regulated, yet the problem persisted. Worse, this smog was fundamentally different from air pollution elsewhere—the yellow, sulfur-dioxide-laced smog that killed 20 people in the Pennsylvania steel town of Donora in 1948, for example, or London's infamous pitch-black "pea-soupers," where the burning of low-grade, sulfur-rich coal added soot to the SO2. (The Great Smog of 1952 would carry off some 4,000 souls in four days.) By contrast, L.A.'s smog was brown and had an acrid odor all its own.
Haagen-Smit had honed his detective skills isolating and identifying the trace compounds responsible for the flavors of pineapples and fine wines, and in 1948 he began to turn his attention to smog.
Chemically, the most characteristic aspect of smog is its strong oxidizing action . . . The amount of oxidant can readily be determined through a quantitative measurement of iodine liberated from potassium iodide solution, or of the red color formed in the oxidation of phenolphthalin to the well-known acid-base indicator, phenolphthalein. To demonstrate these effects, it is only necessary to bubble a few liters of smog air through the colorless solutions. (December 1954)
His chief suspect was ozone, a highly reactive form of oxygen widely used as a bleach and a disinfectant. It's easy to make—a spark will suffice—and it's responsible for that crisp "blue" odor produced by an overloaded electric motor. But there was a problem:
During severe smog attacks, ozone concentrations of 0.5 ppm [parts per million], twenty times higher than in [clean] country air, have been measured. From such analyses the quantity of ozone present in the [Los Angeles] basin at that time is calculated to be about 500 tons.
Since ozone is subject to a continuous destruction in competition with its formation, we can estimate that several thousand tons of ozone are formed during a smog day. It is obvious that industrial sources or occasional electrical discharges do not release such tremendous quantities of ozone. (December 1954)
If ozone really was to blame, where was it coming from? An extraordinary challenge lay ahead:
The analysis of air contaminants has some special features, due to the minute amounts present in a large volume of air. The state in which these pollutants are present—as gases, liquids and solid particles of greatly different sizes—presents additional difficulties. The small particles of less than one micron diameter do not settle out, but are in a stable suspension and form so-called aerosols.
The analytical chemist has devoted a great deal of effort to devising methods for the collection of this heterogeneous material. Most of these methods are based on the principle that the particles are given enough speed to collide with each other or with collecting surfaces . . . A sample of Los Angeles' air shows numerous oily droplets of a size smaller than 0.5 micron, as well as crystalline deposits of metals and salts . . . When air is passed through a filter paper, the paper takes on a grey appearance, and extraction with organic solvents gives an oily material. (December 1950)
Haagen-Smit suspected that this oily material, a complex brew of organic acids and other partially oxidized hydrocarbons, was smog's secret ingredient. In 1950, he took a one-year leave of absence from Caltech to prove it, working full-time in a specially equipped lab set up for him by the LACAPCD. By the end of the year, he had done so.
Through investigations initiated at Caltech, we know that the main source of this smog is due to the release of two types of material. One is organic material—mostly hydrocarbons from gasoline—and the other is a mixture of oxides of nitrogen. Each one of these emissions by itself would be hardly noticed. However, in the presence of sunlight, a reaction occurs, resulting in products which give rise to the typical smog symptoms. The photochemical oxidation is initiated by the dissociation of NO2 into NO and atomic oxygen. This reactive oxygen attacks organic material, resulting in the formation of ozone and various oxidation products . . . The oxidation reactions are generally accompanied by haze or aerosol formation, and this combination aggravates the nuisance effects of the individual components of the smog complex. (November 1962)
Professor of Plant Physiology Frits Went was also on the case. Went ran Caltech's Earhart Plant Research Laboratory, which he proudly called the "phytotron," by analogy to the various "trons" operated by particle physicists. (Phyton is the Greek word for plant.) "Caltech's plant physiologists happen to believe that the phytotron is as marvellously complicated as any of the highly-touted 'atom-smashing' machines," Went wrote in E&S in 1949. "[It] is the first laboratory in the world in which plants can be grown under every possible climatic condition. Light, temperature, humidity, gas content of the air, wind, rain, and fog—all these factors can be simultaneously and independently controlled. The laboratory can create Sacramento Valley climate in one room and New England climate in another." Most of Los Angeles was still orchards and fields instead of tract houses, and the smog was hurting the produce. Went, the LACAPCD, and the UC Riverside agricultural station tested five particularly sensitive crops in the phytotron, Haagen-Smit wrote.
The smog indicator plants include spinach, sugar beet, endive, alfalfa and oats. The symptoms on the first three species are mainly silvering or bronzing of the underside of the leaf, whereas alfalfa and oats show bleaching effects. Some fifty compounds possibly present in the air were tested on their ability to cause smog damage—without success. However, when the reaction products of ozone with unsaturated hydrocarbons were tried, typical smog damage resulted. (December 1950)
And yet a third set of experiments was under way. Rubber tires were rotting from the smog at an alarming rate, cracking as they flexed while rolling along the road. Charles E. Bradley, a research associate in biology, turned this distressing development into a cheap and effective analytical tool by cutting rubber bands by the boxful into short segments. The segments—folded double, secured with a twist of wire, and set outside—would start to fall apart almost before one could close the window. "During severe smog initial cracking appears in about four minutes, as compared to an hour or more required on smog-free days, or at night," Haagen-Smit wrote in the December 1954 E&S.
The conclusion that airborne gasoline and nitrogen oxides (another chief constituent of automobile exhaust) were to blame for smog was not well received by the oil refineries, who hired their own expert to prove him wrong. Abe Zarem (MS '40, PhD '44), the manager and chairman of physics research for the Stanford Research Institute, opined that stratospheric ozone seeping down through the inversion layer was to blame. But seeing (or smelling) is believing, so Haagen-Smit fought back by giving public lectures in which he would whip up flasks full of artificial smog before the audience's eyes, which would soon be watering—especially if they were seated in the first few rows. By the end of his talk, the smog would fill the hall, and he became known throughout the Southland as Arie Haagen-Smog.
By 1954, he and Frits Went had carried the day.
[Plant] fumigations with the photochemical oxidation products of gasoline and nitrogen dioxide (NO2) was the basis of one of the most convincing arguments for the control of hydrocarbons by the oil industry. (December 1954)
It probably didn't hurt that an outbreak that October closed schools and shuttered factories for most of the month, and that angry voters were wearing gas masks to protest meetings. By then, there were some two million cars on the road in the metropolitan area, spewing a thousand tons of hydrocarbons daily.
Incomplete combustion of gasoline allows unburned and partially burned fuel to escape from the tailpipe. Seepage of gasoline, even in new cars, past piston rings into the crankcase, is responsible for 'blowby' or crankcase vent losses. Evaporation from carburetor and fuel tank are substantial contributions, especially on hot days. (November 1962)
Haagen-Smit was a founding member of California's Motor Vehicle Pollution Control Board, established in 1960. One of the board's first projects was testing positive crankcase ventilation (PCV) systems, which sucked the blown-by hydrocarbons out of the crankcase and recirculated them through the engine to be burned on the second pass. PCV systems were mandated on all new cars sold in California as of 1963. The blowby problem was thus easily solved—but, as Haagen-Smit noted in that same article, it was only the second-largest source, representing about 30 percent of the escaping hydrocarbons.
The preferred method of control of the tailpipe hydrocarbon emission is a better combustion in the engine itself. (The automobile industry has predicted the appearance of more efficiently burning engines in 1965. It is not known how efficient these will be, nor has it been revealed whether there will be an increase or decrease of oxides of nitrogen.) Other approaches to the control of the tailpipe gases involve completing the combustion in muffler-type afterburners. One type relies on the ignition of gases with a sparkplug or pilot-burner; the second type passes the gases through a catalyst bed which burns the gases at a lower temperature than is possible with the direct-flame burners. (November 1962)
Installing an afterburner in the muffler has some drawbacks, not the least of which is that the notion of tooling around town with an open flame under the floorboards might give some people the willies. Instead, catalytic converters became required equipment on California cars in 1975.
In 1968, the Motor Vehicle Pollution Control Board became the California Air Resources Board, with Haagen-Smit as its chair. He was a member of the 1969 President's Task Force on Air Pollution, and the standards he helped those two bodies develop would eventually be adopted by the Environmental Protection Agency, established in 1970—the year that also saw the first celebration of Earth Day. It was also the year when ozone levels in the Los Angeles basin peaked at 0.58 parts per million, nearly five times in excess of the 0.12 parts per million that the EPA would declare to be safe for human health. This reading even exceeded the 0.5 ppm that Haagen-Smit had measured back in 1954, but it was a triumph nonetheless—the number of cars in L.A. had doubled, yet the smog was little worse than it had always been. That was the year we turned the corner, in fact, and our ozone levels have been dropping ever since—despite the continued influx of cars and people to the region.
Haagen-Smit retired from Caltech in 1971 as the skies began to clear, but continued to lead the fight for clean air until his death in 1977—of lung cancer, ironically, after a lifetime of cigarettes. Today, his intellectual heirs, including professors Richard Flagan, Mitchio Okumura, John Seinfeld, and Paul Wennberg, use analytical instruments descended from ones Haagen-Smit would have recognized and computer models sophisticated beyond his wildest dreams to carry the torch—a clean-burning one, of course—forward.

By Douglas Smith

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