Chapter 12—Organic Pollutants 12.

1 Organic Compounds In The Atmosphere: effects divided into two categories • Direct Effects: such as cancer caused by exposure to vinyl chloride. • The formation of Secondary Pollutants such as photochemical smog. • Loss of Organic Substances from the Atmosphere: dissolution in precipitation, dry deposition, photochemical reactions, incorporation in particulate matter, and uptake by plants. • Forest Trees have a very large surface area exposed to the atmosphere, and remove a large quantity of organic material from air. The cuticle layer of plants is lipophilic, meaning that it has an affinity for organic matter. • Global Distillation and Fractionation of Persistent Organic Pollutants: the least volatile persistent organic compounds are deposited relatively near their sources. The more volatile compounds are transported to the polar regions

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where they are condensed. This may have important implications with respect to the accumulation of persistent organic compounds in the fragile polar environment. Volatility is a function of vapor pressure. Vapor pressure is the pressure exerted by a particular compound at a particular temperature. The vapor pressure is always equal to the ambient pressure at a substances boiling point. For example, at 100° C, the vapor pressure of water is 1 atm. This is the boiling point of water at 1 atm. At 12,000 ft of elevation (base camp for climbing Long’s peak), atmospheric pressure drops to 0.65 atm. At this altitude, water boils at 88.4°C, making it impossible to brew good coffee. Vapor pressure is usually estimated using the Antoine Equation. This equation is based on the Clausius-Clapeyron equation. Generally, the constants for a particular substance can be looked up, or they can be calculated with one vapor pressure point and the boiling point. Note that the Antoine Equation, while suitable for most organics, does not work well for water. The numbers presented above were calculated from the steam tables.

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ln( Pv ) A

B T C

atm mmHg 1. 760

A B C Pv

16.0381 3110.79 56.16 exp A B T C . mmHg Pv = 21.495 mmHg Pvi exp A B Ti C i 0 .. 114 Ti 273.15 i T 273 23 Antione constants for 1,1,2 trichloroethane, from SPR p637.

convert tempertaure to Tabs.

1,1,2- TCA, vapor pressure v. T
800 720 640 560 Pv 480 i 400 320 240 160 80 0 0 12 24 36 48 T i 60 273.15 72 84 96 108 120

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12.2 Organic Compounds from Natural Sources: hydrocarbons generated by human activity constitute only 1/7th of the total hydrocarbons in the atmosphere. The principle natural contribution is methane produced by anaerobic bacteria in water, sediments and soil. • Flatulent emissions from animals add about 85 million metric tons of methane per year. • Rice fields add about 100 million metric tons of methane per year. • Methane is present at about 1.4 ppm in the troposphere. • Biogenic Hydrocarbons are hydrocarbons produced by living sources. Other natural sources are forest fires and volcanoes. • Plants give off ethylene (C2H4). Ethylene functions as a “messenger” regulating plant growth. The double bond makes ethylene reactive with HO· and with oxidizing species present in the atmosphere. Is ethylene reactive with 1O2? • Plants also give off terpenes. Terpenes are natural compounds based on the isoprene structure.

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Biological formation of the terpenes occurs by the combination of two molecules of acetic acid to give mevalonic acid (C6H12O4) and conversion of the latter to isopentenyl pyrophosphate, which contains the five-carbon isoprene skeleton. Further transformations of the isopentenyl compound yield the true terpenes and the terpenoids. Copyright © 1994-2000 Encyclopædia Britannica, Inc_

Environmental Chemistry, 7th Edition, Stanley E. Manahan. Lewis Publishers, Boca Raton, 1999.

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• The double bond(s) in terpenes makes them highly reactive with HO· and with oxidizing agents, especially ozone.

• A great variety of esters are released by plants. These have little significance, but smell nice.

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12.3 Pollutant Hydrocarbons: hydrocarbons are widely used as fuels; therefore they predominate among organic atmospheric pollutants. • Hydrocarbons in automobile exhaust are about 1/3 alkanes, 1/3 alkenes and 1/3 aromatic hydrocarbons. The last two are fairly reactive. • Alkanes are attacked in the atmosphere by HO·, resulting in the formation of an alkyl radical, CxH2x+1·. • The alkyl radical reacts with O2 to form an alkylperoxyl radical, CxH2x+1O2·. • The alkylperoxyl radical may oxidize NO to NO2, while also forming the alkoxyl radical, CxH2x+1O·.

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• Alkenes enter the atmosphere from engine exhaust, foundry operations and petroleum refineries. The ones shown below are among the top 50 chemicals produced, with annual production of several billion kg. Alkenes are highly reactive in the presence of NOx and sunlight. They also react with HO·, which add across the double bond. Ozone also adds across double bonds, and may produce aldehydes.

NO3 also reacts with alkenes, but more slowly than HO·. Formaldehyde is formed.

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12.4 Aryl Hydrocarbons: compounds with only one benzene ring and PAHs.

These are in the “top 50.”

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• Single ring compounds are constituents of lead-free gasoline. • Biphenyls, and other unconjugated rings, are compounds emitted in diesel smoke. These compounds are also found in tobacco smoke. • PAHs are usually present as aerosols because of their low vapor pressure. • Reactions of Aryl Hydrocarbons • Addition of HO· results in the formation of an unstable radical:

This radical can react with O2 to form phenol and a reactive hydroperoxyl radical.

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At night, aryl compounds can react with NO3 It has been found that the tendency of gasoline vapor to form aerosols is attributable to the aromatic hydrocarbon fraction of the gasoline. 12.5 Aldehydes and Ketones

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• The most common carbonyl compound is formaldehyde:

• Formaldehyde is produced by atmospheric hydrocarbons reacting with HO· to form the methoxy radical, followed by reaction with O2. • Annual industrial production exceeds 1 billion kg. Formaldehyde is used in plastics, resins, lacquers, dyes and explosives. It is also used in the manufacture of phenol, urea and melamine plastics, and for formaldehyde

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based adhesives in wood products such as particleboard and plywood. It is used extensively in mobile home construction. • Other important aldehydes:

• Aldehydes enter the atmosphere from engine exhaust, incinerator emissions, spray painting, polymer manufacture, printing, petrochemicals and lacquer manufacture. • Aldehydes are second to NO2 as sources of free radicals from photo absorption. The carbonyl group is termed a chromophore. It absorbs in the near-uv region of the spectrum, and forms a formyl radical.

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• Aldehydes are precursors to the production of the powerful oxidant peroxyacyl nitrates (PANs).

• Ketones: The most abundant atmospheric ketone is acetone. Half of the acetone in the atmosphere comes from the oxidation of alkanes and alkenes in

the atmosphere. Most of the rest comes from biogenic emissions and burning. Only about 3% is anthropogenic. 12.6 Miscellaneous Oxygen-Containing compounds • Alcohols: methanol, ethanol, isopropanol and ethylene glycol are among the top 50 chemicals, with annual production of about a billion kg.
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Mostly used for the manufacture of chemicals. MeOH is used to make formaldehyde, as a solvent and as antifreeze. EtOH is used as a solvent and as a starting material for acetaldehyde, acetic acid and many other chemicals. Ethylene glycol is used for antifreeze. • Ethers—highly explosive, otherwise not of great interest. • Oxides—among the 50 most widely produced industrial chemicals. Ethylene oxide is toxic, carcinogenic, and explosive. Not significant as a pollutant. • Carboxylic Acids—low vapor pressures and high water solubility. Not present in the atmosphere to a great extent. 12.7 Organohalide Compounds: may be alkyl halides, alkenyl halides, or aryl

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halides. • vinyl chloride is used to make PVC pipe. It is carcinogenic. • Trichloroethylene (TCE) is a degreasing and dry-cleaning solvent.

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• Lighter organohalides are most likely to be found in the atmosphere. • Chlorofluorocarbons (CFCs) used as working fluids for air conditioning and for blowing foam. These reach the stratosphere to participate in the destruction of ozone. They are highly inert and were produced at the level of about one half million tons per year. In 1974 Molina and Rowland received the Nobel Prize for showing that CFCs could destroy stratospheric ozone. In the upper atmosphere, where sufficiently short wavelength light is available, CFCs are photo disassociated:

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The introduction of hydrogen containing fluorocarbons allows the destruction of these compounds in the troposphere by OH·. R-134a is 1,1,1,2 tetrafluoroethane.

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• Halons are bromine containing hydrocarbons used as fire extinguishers. • Perfluorocarbons: Several hundred metric tons of CF4 is used annually as an etchant in plasma reactors in the semiconductor industry. 30,000 metric tons is used annually in the aluminum refining industry. • These compounds do not react with HO·. They are only disassociated by light of less than 130 nm. CF4 has an estimated lifetime of 50,000 years. • They are powerful greenhouse gases. • Chlorinated Dibenzo-p-dioxins and Dibenzofurans: These highly toxic compounds come from automobile exhaust, waste incinerators and steel and other metal production. Carbon fly ash may catalyze the formation of these compounds at as low a temperature as 300° C. They are mostly present in atmospheric particulate matter. 12.8 —Read 12.9 Organonitrogen Compounds: amines, amides, nitriles, nitro compounds, heterocyclic nitrogen compounds

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• Amines: NHxRy • Low molecular weight amines smell like rotting fish. • Aryl amines are known to cause cancer (bladder). Aryl amines are used as antioxidants and curing agents in plastics manufacture, in drugs, pesticides, dyes, pigments and inks.

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• Amines are attacked by HO· and, being basic, may interact with acidic gases in precipitation. • Amides: (analogous to ester, but with nitrogen in place of single bonded oxygen) The most common industrial amide is dimethylformamide (DMF), also dimethylacetamide (DMAC). These are used as solvents and plasticizers. They are also skin transport agents (in liquid form), behaving similar to DMSO.

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• Nitriles—organic cyanide group (-C≡N-) acetonitrile and acrylonitrile. Most nitriles of atmospheric significance are low molecular weight. Acrylonitrile is the monomer for polyacrylonitrile. It is the only nitrogencontaining chemical in the top 50 industrial chemicals. • Nitro compounds -- RNO2: Nitromethane, nitroethane and nitrobenzene. Peroxyacetyl nitrate (PAN) is the end product of photochemical oxidation of hydrocarbons in polluted atmospheres. • Heterocyclic nitrogen compounds, such as pyridine and pyrrole are generated in tobacco smoke. They can reasonably be expected to occur in the smoke of other burning vegetation. • Nitrosamines—R2N-N=O: carcinogenic compounds (remember bacon?) that have been found in the atmosphere. Problems: 1-7

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