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Reactions at the earths surface

Geochemistry of the earths surface is dominated by aqueous solution and their interactions with rock. In this chapter, we focus on water and its interaction with solids at the Earths surface

We can broadly distinguish two kinds of aqueous solutions: 1) Continental water: ground water, fresh surface waters (river, stream and lake waters), and saline lake waters. 2) Seawater

Hydrothermal fluids are third class of water produced when water is heated and undergoes accelerated interactions with rock and often carry a much higher concentration of dissolved constituents than fresh water.

Redox in Natural Waters

The surface of the Earth represents a boundary between regions of very different redox state. The atmosphere contains free oxygen and therefore is highly oxidizing In the Earths interior, however, there is no free oxygen Natural waters exist in this boundary region and their redox state, perhaps not surprisingly, is highly variable. Biological activity is the principal cause of the different redox state. The redox state of solutions and solids at the Earths surface is largely governed by the balance between photosynthesis and respiration.

Water in equilibrium with atmospheric oxygen has a pe of +13.6 (at pH = 7). At this pe, thermodynamics tells us that all carbon should be present as CO2 (or related carbonate species), all nitrogen as NO3 -, all S as SO4 2 -, all Fe as Fe3+, and all Mn as Mn4+.

The relation between p and pw is simply:

Reactions are ordered by decreasing pw from strong oxidants at the top to strong reductants at the bottom. In this order, each reactant can oxidize any product below it in the list, but not above it. Thus sulfate can oxidize methane to CO2, but not ferrous iron to ferric iron.

Biogeochemical Redox Reactions

photosynthesis and atmospheric exchange maintains a high p in surface waters. Once oxygen is consumed, a variety of specialized bacteria continue to consume organic matter and respire utilizing oxidants other than oxygen. Thus p will continue to decrease.

Figure 13.1. Important biogeochemical redox couples in natural waters.

Eutrophication

The extent to which the redox sequence depends on a several factor: 1. Temperature structure 2. Nutrient levels

In lakes with high nutrient levels: Regions where dissolved oxygen is present are termed oxic, those where sulfide or methane are present are called anoxic. Regions of intermediate p are called suboxic. Lakes are where suboxic or anoxic conditions exist as a result of high biological producitivy are said to be eutrophic. The process is called eutrophication

Redox Buffers and Transition Metal Chemistry

The behavior of transition metals in aqueous solutions and solids in equilibrium with them is particularly dependent on redox state. Many transition metals have more than one valence state within the range of p of water. Redox conditions influence a strong control on the concentrations of these elements in natural waters.

For the example: Fe and Mn There two common circumstances where higher Fe and Mn concentrations in water occur: 1) The first is when sulfide ores are exposed by mining and oxidized to sulfate 2) The second circumstance where higher Fe and Mn concentrations occur is under suboxic or anoxic conditions that may occur in deep waters of lakes.

Weathering, Soils, and Biogeochemical Cycling

Weathering is the process by which rock is physically and chemically broken down into relatively fine solids (soil or sediment particles) and dissolved components. Weathering plays a key role in the exogenic geochemical cycle (i.e., the cycle operating at the surface of the Earth). Weathering related to atmospheric CO2

What are the factors that control on weathering rates? 1) Temperature (Berner et al. (1983) and Berner (1991)) 2) Tectonic uplift and exposure of fresh rock (Edmond et al. (1995))

Soil Profiles

Chemical Cycling in Soils

Biogeochemical Cycling

The biota plays a substantial role in the weathering process and in controlling the composition of streams.

The biota will influence both soil and water chemistry within a water-shed and can be a significant reservoir for some elements.

There are four sources of nutrients in an ecosystem: 1) The atmosphere 2) Dead organic matter 3) Water 4) Rock

WEATHERING RATES AND REACTIONS

The Watershed Approach