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RUSSELL R. DICKERSON
Sandstone portal Figure on Herten Castle in Ruhr district of Germany. Sculpted 1702; photographed in 1908.
VII.ACID DEPOSITION
See Turco, Ch. 9 Finlayson-Pitts & Pitts, Part 6 Seinfeld & Pandis Ch. 20
Introduction
The industrial revolution greatly increased the amount of acid in the atmosphere. These acids accelerate the rate of weathering of both natural and man-made materials. (Figures of sandstone Madonna). Today we will discuss what acid deposition is, what its effects are, the chemistry and physics of formation and transport, and who is responsible for it.
History As early as 1852, R. A. Smith analyzed rain that near the industrial city of Manchester, England and found that urban aerosol particles tend to be composed primarily of sulfuric acid, but as the air is transported away from sources over more rural areas, the acid is neutralized by absorption of ammonia. urban suburban rural HSO + NH (NH)HSO (+NH) (NH)SO sulfuric acid ammonium bisulfate ammonium sulfate
Throughout the early part of the twentieth century, European scientists documented the sources and effects of atmospheric acids. It was not until 1958 that acidity of precipitation in the US was characterized (Junge and Werby, 1958)
A soils capacity to exchange base ions for those in solution (cation exchange capacity) is a measure of potential fertility. The impact of acids on soil fertility depends on the structure and composition of the clays in the soil. Maryland has serveral geological regimes with varying sensitivities to acid deposition (Figure). Forests can be especially sensitive to nutrient loss. In Europe in 1993 abou ta quarter of the trees have died or are more than 25% defoliated. This Waldsterben or forest death has been attributed at, least in part, to environmental degradation from a combination of acid deposition, ground-level ozone, and excess nutrification, primarily nitrogen. In the US, loss of forests has been so dramatic, although several species including ash and oak are sensitive to acidification of soils.
2 2H Ca 2 CO 3 CO 2 Ca 2
The sensitivity surface waters depends critically on their neutralizing or buffering capacity. Alkaline materials such as CaCO, and MgCO can neutralize acids.
The surface of the American Midwest is predominantly limestone (CaCO), and lakes and streams have high neutralizing capacity. In the East granite dominates; soils and surface waters lacking buffering capacity, are highly sensitive to acidification.
Salt Waters The Ocean is strongly pH buffered, has a high sulfate content naturally, and is relatively insensitive to acid rain. Over much of the ocean, however, nitrate is the limiting nutrient for biological activity. Addition of nitrogen from the atmosphere can increase primary productivity, and the consequences reverberate throughout the ecosystem. The Chesapeake Bay is particularly sensitive to excess nutrients. Additional nitrate or ammonium from atmospheric deposition to the Bay or its watershed contributes to the problem of excess eutrophication. Nitrate allows thick beds of aquatic layers of the waters. Loss of higher animals follows.
Materials The Taj Mahal, the friezes on the Parthenon, the Madonna in Herten, Germany, and the Lincoln Memorial are made of marble. Marble, a particular crystalline form of calcite (CaCO), and sandstone (grains of sand held together by calcite), are subject to attack by sulfuric acid.
Origins Primarily power generation and ore smelting (pie charts). For example nickel is mined as nickel sulfide, NiS. In smelting, it is heated in air (Sudbury, Canada).
NiS O 2 Ni SO 2
The molecular weight of nickel is 57 g/mole, so smelting produces more than a ton of SO for each ton of nickel produced. d) Formation and Composition Gas Phase production of nitric acid: OH + NO + M HNO + M Aqueous phase production of nitric acid: NO + O NO + O NO + NO + M = NO + M NO + HO(l) 2HNO(aq)
This process is important only at night, and when air temperatures are low because the formation of NO is reversible, and the equilibrium coefficient is highly temperature dependent. Also, NO is rapidly photolyzed by visible radiation. NO + hv NO + O Gas Phase production of sulfuric acid: OH + SO + M HOSO + M Aqueous phase production of sulfuric acid: SO + HO HSO Lifetime and Transport Wet vs dry deposition
Problem Solving 1. European community requirements: 2.0 g/m3 and 0.4 g/m3 if coal is 0.5 to 7% S by weight, can such goals be met by buying low sulfur coal?? 2 2. Calculate the pH of a solution of 10 M SO 4 and 10 m NO3 3. From the mean pH of 4.1, and the assumption of equal molar nitrate and sulfate, estimate the molarity of nitric and sulfuric acids in College Park. 4. Estimate the rate of dry deposition for a give PBL height, and concentration of HSO and HNO. 5. If rainout plus washout is 50% efficient, what would have to be precipitation frequency for there to be equivalent amounts of wet and dry acid deposition?
NO3
OH
10 64 dep 27 dry 20 wet dep 6 dry 44 wet
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