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Environmental Geochemistry DM Sherman, University of Bristol

2005/2006

Acidification of Soil and Surface Water (Acid Rain)


Environmental Geochemistry University of Bristol

pH of Surface Water as Buffered by the Atmosphere...


What is the pH of a surface water in equilibrium with the atmosphere given the atmosphere has a PCO2 = 10-3.5 bar? The reaction CO2(g) + H2O = H2CO3 has a pK = 1.46: 10-1.46 = [H2CO3]/PCO2 so that [H2CO3] = 10-5.0 H2CO3 will dissociate to form protons and HCO3-: K=10-6.35 = [H3O+][HCO3-]/[H2CO3] to give [H3O+] = 2.1 x 10-6 so that pH = 5.67.

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Environmental Geochemistry DM Sherman, University of Bristol

2005/2006

Acid Precipitation
Acid rain is atmospheric precipitation at pH = 4.0-4.4 Atmospheric pollutants NO2 and SO2 generated by coal-fired power plants react with photochemically generated OH. radicals to give HNO3 and H2SO4 aerosols: SO2 + OH HOSO2 HOSO2 + O2 HO2 + SO3 SO3 + H2O H2SO4 NO2 + OH HNO3

Consequences of Acid Precipitation

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Environmental Geochemistry DM Sherman, University of Bristol

2005/2006

Characteristics of acidified lakes

Burnmoor Tarn

Extent of Acid Rain in Europe

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Environmental Geochemistry DM Sherman, University of Bristol

2005/2006

pH of Atmospheric Deposition UK
The susceptibility of soils to damage by acid rain is strongly dependent upon the bedrock lithology: Limestone and chalk deposits are not susceptible to acidification. Rocks containing Al minerals such as feldspar, muscovite, are more susceptible.

Consequences of Acidification
(In Soils) In soils, increased acidity releases Al into the soil solution (as Al3+, Al(OH)n3-n). The excess Al damages root hairs of plants. 2H+ + 3KAlSi3O8 + 3H2O = Al2Si2O5(OH)4 + 7SiO2 +Al(OH)4- + 3K+ Acid input also releases cations such as K, Ca, Mg from smectite clays and decreases soil fertility. H+ + K(Mg0.5Al3.5)(Al0.5Si7.5)O20(OH)4 = H(Mg0.5Al3.5)(Al0.5Si7.5)O20(OH)4 + K+

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Environmental Geochemistry DM Sherman, University of Bristol

2005/2006

Consequences of Acidification (cont.)


Release of Al also leads to the formation of AlPO4 (at low pH) and limits phosphate bioavailability. At higher pH, Al(OH)3 and related phases sorb HPO4-2 by surface complexation. Lack of phosphate may keep lakes in an oligotrophic state.

Consequences of Acidification
(In lakes) Trout cannot live at pH < 5.0. In lakes, increased acidity releases Al into solution (as Al3+, Al(OH)n3-n). Al is toxic to fish.

Normal fish gill

Damaged fish gill with Al ppt. (stained blue).

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Environmental Geochemistry DM Sherman, University of Bristol

2005/2006

Acid-base Buffers in Soils


Carbonate buffers (pH > 7) H+ + CO32- = HCO3Exchangeable base cation buffering H+ + Ca0.5(Mg0.5Al3.5)(Al0.5Si7.5)O20(OH)4 = H(Mg0.5Al3.5)(Al0.5Si7.5)O20(OH)4 + 0.5Ca2+ Aluminosilicate dissolution 2H+ + 3KAlSi3O8 + 3H2O = Al2Si2O5(OH)4 + 7SiO2 +Al(OH)4- + 3K+

Buffering of soil pH by mineral dissolution

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Environmental Geochemistry DM Sherman, University of Bristol

2005/2006

Solubility of Al vs. pH

The aqueous aluminum concentration that may result from acidification is a function of the major mineralogy of the host rock.

Aqueous Speciation of Al

Positive cations (Al3+, Al(OH)2+ and Al(OH)2+) may act as exchangeable cations in clay interlayers. Alhydroxy ions may also sorb to mineral surfaces..

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Environmental Geochemistry DM Sherman, University of Bristol

2005/2006

Characteristics of non-acidified lakes

An Acidied Lake: Loch Grannoch

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Environmental Geochemistry DM Sherman, University of Bristol

2005/2006

Summary
Buffer capacity of a lake/soil to acidification is dependant upon the mineralogy of the rock. Major problem results from dissolution of Al under acidic conditions. Acidification is believed to be improving in the UK due to emission controls.

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