Nitric acid, atmospheric deposition

Nitric acid undergoes both wet and dry deposition rapidly and can be neutralized by ammonia, the major gaseous base found in the atmosphere. As discussed in Section E.2, the neutralization reaction is an equilibrium reaction so that by itself, this does not result in permanent removal from the atmosphere. However, as seen in this chapter and in Chapter 9, this acid-base reaction has some important implications for visibility in the atmosphere and for the nitrate concentrations found in respirable particles. 

While the focus in terms of acid deposition has been on sulfuric and nitric acids, it has been increasingly recognized that organic acids can also contribute significantly to the acidity of both the gas and aqueous phases in both urban and remote regions. A review of carboxylic acids in the atmosphere is given by Chebbi and Carlier (1996). 

Storm water runoff from cities and villages presents another problem. This runoff contains salts from road deicing, street refuse, animal waste, food litter, residue from atmospheric deposition of sulfuric and nitric acid, metals, asbestos from automobile brakes, rubber from tires, hydrocarbons from motor vehicle exhaust condensates, oil and grease, soil and inorganic nutrients from construction sites, and a variety of other chemicals. Research shows a heavy impact of urban nonpoint pollution on freshwater quality (World Resources Institute, 1988). 

Scientists have discovered that air pollution from the burning of fossil fuels is the major cause of acid rain. Acidic deposition, or acid ram, as it is commonly known, occurs when emissions of sulfur dioxide (SO ) and oxides of nitrogen (NOx) react in the atmosphere with water, oxygen, and oxidants to form various acidic compounds. This mixture forms a mild solution of sulfuric acid and nitric acid. Sunlight increases the rate of most of these reactions. 

Ruthenium Dicarbonyl, Ru(CO)a.—Ruthenium, like iron, yields a carbonyl derivative. It is obtained as an orange-yellow deposit upon subjecting ruthenium black to the action of carbon monoxide at 300° C. under a pressure of 400 atmospheres. The product is extracted from the residue by solution in alcohol. It is insoluble in benzene and in hydrochloric acid, but soluble in nitric acid and in bromine, gas being evolved. When heated, a mirror of metallic ruthenium is produced.5 In contradistinction to the other carbonyls of this group of metals ruthenium dicarbonyl is not volatile. 

For some trace gases, for example, nitric acid vapour, dry deposition represents a major sink mechanism. In this case the process may have a major impact upon atmospheric lifetimes. 

Extrapolation to the K/T boundary requires consideration of the time scales of acid deposition. Nitric acid formation occurs rapidly by aqueous phase reaction of NO and NO2 with liquid water produced by tlie incident K/T bolide on both impact and infall of ejecta. For tlie quantities of NO produced by the K/T impact ( 10 5 moles), conversion to HNO3 occurred wiUiin days, assuming sufficient liquid water was available in the posl-K/T atmosphere. The nitric acid will form an acid rain of pH 0 for a liquid water content of 1 g/m (typical of tropospheric clouds) but will contain enough protons to weather only 3 x 10 moles of Sr, for Sr/(Ta -0.003 in soil and bedrock minerals. Sulfuric acid formation occurred on a time scale of years [7] due to the slow rate of gas phase SO2 oxidation. Spread evenly over 10 years, 10 moles of SO2 produced a global acid rain of pH —4, and released —3 x 10 moles of Sr. 

FIGURE 4-39 The acid deposition process. Acid precursors, notably oxides of nitrogen and sulfur, are emitted to the atmosphere, primarily by fuel-burning equipment. Acid precursors are oxidized in the atmosphere to nitric and sulfuric acids by a variety of homogeneous and heterogeneous reactions. The acids are deposited by precipitation-related processes such as washout and rainout, by sorption of nitric acid vapor, and by dry deposition of acidic particulate material such as ammonium sulfate aerosol. (Stern et ah, 1984.)... 

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