Reactions and Processes Influenced by Soil Wetness Topics for Consideration A.Organic matter (OM) accumulation B.Some reduction effects induced by soil saturation C.Redoximorphic features D.Calcium carbonate accumulation at surface (marl) E.Near-surface stratification (with special morphology) F.Root death

Reactions and Processes Influenced by Soil Wetness A. Organic Matter (OM) Accumulation OM accumulation favored by near-surface saturation. Why? - Greater biomass production - Lower T - Anaerobic pathways << aerobic pathways in energy yield - Anaerobic decomposition therefore much slower - Possible limited availability of electron acceptors - Fewer fragmenting fauna and bacterial grazers

Consequently, wetland soils tend to have - Higher OM content - Lower value & chroma in surface horizons - Thicker surface horizons than associated upland soils. Caveats - Climate and vegetation affect OM-wetness link - Hydric indicators are therefore region specific - Hydric indicators can require more evidence (e.g., 70% coatings on sand grains) - Muck more definitive than mucky peat or peat in FL.

tricky questions - Would "A" horizons of hydric soils commonly consist of organic soil material? - Could a hydric soil have a mineral surface horizon? - Could a mineral soil have organic soil materials? (This sounds straightforward, but actually it’s ambiguous. I’ll explain why) - Could an organic soil ever NOT be a hydric soil?

What is “saturation”? Saturation occurs where free water is present in the soil. The water in the soil has a pressure that is equal to or greater than atmospheric pressure (Soil Survey Staff. 1999). A soil is saturated where water fills a well or recently dug hole. B. Some Reduction Effects Induced by Saturation

What does “reduced” mean? Reduced is a vague term meaning that reduced forms of oxygen, nitrogen, manganese, iron, sulfur, and/or carbon are present in the soil solution unless a specific element is specified. In the wet soil arena “reduction” has come to mean that reduced iron is in solution. This is because of the importance iron plays in soil morphology and the relative ease of measuring for reduced iron.

Points of departure - a generalized reduction equation, a (oxidants) + b H+ + n e- = c (reductants) + d H2O - and the Nernst equation (as stolen from Dr. Reddy) where Eh is electrode potential (calibrated to Pt/H2, mV), E 0 is standard electrode potential (unit activity, STP), R is gas constant, T is temperature (K), F is Faraday constant, n = number of electrons transferred, and [ ] is activity of chemical species in mol/L.

-The Nernst equation shows an increase in pH requires a decrease in Eh, all else being equal. - Half-cell reduction reactions at Ph 7 for successive (top to bottom) electron acceptors in soils include: Eh (mv) 24e - + 6O 2 +24H + = 12H e H + + 2NO 3 - = N 2 + 6H 2 O e - + 4H + + MnO 2 = Mn H 2 O e - + 3H + + Fe(OH) 3 = Fe H 2 O e - +10H + + SO 4 2- = H 2 S + 4 H 2 O e - +8 H + + CO 2 - = CH H 2 O The next slide shows the redox state for two of these elements (Oxygen and Iron).

pH4 pH5 pH6 pH7 pH8 Iron is reduced Iron is not reduced Oxygen is not reduced Oxygen is reduced Eh

Redox measurements enable these reactions to be expressed in terms of the Nernst equation. Two examples are: Eh = log (Mn2+) pH Eh = log (Fe2+) pH (for FeOOH) We can infer that: - Eh and pH are inversely related - Slope is slightly more negative (steeper) for Fe - Intercept is indeterminate without knowing metal activities - For comparable reduced species activities, Mn more easily reduced.

Eh vs. pH plots would have the following trends: (Not so) trick question: - What are the implications of the above Eh vs. pH plot for Fe-related morphological indicators of wetness in alkaline soils?

Morphological implications: - Reduced Fe and Mn are soluble and colorless - Mn oxides are black - Fe oxides range from red to yellowish brown - Fe and Mn distributions are influenced by spatial and temporal variability in redox conditions - Morphological consequence - Redoximorphic Features Olfactory implications - Hydrogen sulfide odor for very reduce conditions (e.g. coastal marshes, where seawater supplies SO4)

Measuring Reduction in Soils Methods –Analyzing of soil solution for reduced form of nitrogen, manganese, iron, sulfur, and/or carbon - too expensive except for research –Using dyes is sometimes good for routine field work. Solutions change color when they encounter reduced iron. Most common is  -dipyridyl. When solution is sprayed onto a fresh slice of soil it turns red almost immediately if reduced iron is present. Will not work where soils are low in iron such as much of Florida. –Measuring redox potential is complex but can be done in field. More on this method later –Measuring dissolved oxygen - too expensive except for research.

Using  -dipyridyl dye  -dipyridyl applied to fresh slice of soil –(1, on photo ) where no reduced iron is present and (2) where reduced iron is present and the soil turned red.

Measuring Redox Potential Redox reactions create an electrical potential and the difference in electrical potential between the soil as determined through use of a platinum electrode and a reference electrode (both of which are in contact with soil solution) can be measured. On the next slide the basic equipment needed to measure redox potential in soil are shown (platinum electrode, reference electrode, and volt meter). Normally 5 replicate readings are required because Eh measurements are variable. Reduction reactions occur when soil solution is at various redox potentials. These reactions also vary with pH and mineral species present.

Measuring Redox Potential (cont.) Platinum Electrode Reference Electrode Volt meter Soil Air

Factors Controlling Reduction in Soils 1.Organic matter must be present (source of electrons). –Dead roots –Plant debris such as leaves –Pieces of roots –Root exudates –Dissolved organic carbon 2. Air must not enter the soil (soil is saturated). 3. Organisms must be decomposing organic matter. This activity is termed “microbial active.” For most of the US, wet soils are microbial active throughout the year. 4. Dissolved oxygen in soil water must be removed.

Water Movement and Reduction Reduction occurs where water moves through soil slowly and occurs best where water does not move through the soil and most all pores are filled with water. Reduction does not occur where water flows too quickly. Fast moving water (right photo) carries oxygen which must be removed before reduction of other elements can occur. Soil may be saturated but not reduced if: –1 organic matter content is low (less than about 2 percent), –2. microbial activity is lacking, and/or –3. water moves too quickly (oxygen is not removed).

Summary of Features Formed by the Redox Reactions Reducing/oxidation reactions, collectively known as redox reactions, leave signs in the soil that they have occurred as follows: Element Sign that Reduction Occurred OxygenCarbon Accumulation/Differential Removal* NitrogenNone Manganese Redoximorphic Features** IronRedoximorphic Features** SulfurRotten egg odor –*Remember this is an aerobic reduction reaction. It is the first reducing reaction. The soil is anaerobic after most all of the oxygen has been reduced and microbes start reducing nitrogen. –**A generalized term which included all the features produced by manganese and iron reduction reactions.

Reduction Sequence Products: A Haiku water nitrogen manganous ferrous sulfide swampy methane gas This haiku (Hurt. 2000) provides reduction sequence products in the order they are produced after a soil is saturated. Haiku (either singular or plural) is defined as: an unrhymed verse form of Japanese origin with three lines containing usually 5, 7, and 5 syllables respectively; also, a poem in this form usually has a seasonal reference ( Most haiku that address soils would be poems.

C. Redoximorphic Features What are they? Why are they important? What do they look like? How do they form?

What are redoximorphic features? –Features associated with wetness which result from alternating periods of reduction and oxidation of Fe and Mn in soils. –Qualification: Should be validated regionally. Why are they important? –As indicators that soil has been saturated, even if not saturated at the time observed!

What do they look like? Types of redoximorphic features: a.Redox Concentrations (i))Nodules and Concretions (ii)Masses (iii)Pore Linings b.Redox Depletions (i))Iron Depletions (i)Clay Depletions c.Reduced Matrix

Nodules Examples of redox concentrations and depletions

Fe & Mn can be redistributed in same soil horizon.

Colors are revealing about soil drainage!

How do Redoximorphic Features Form? Involves 5 components (Review): –Organic matter: electron source. –Microbes: electron “brokers”. –Oxygen: ultimate electron acceptor. –Redox-sensitive metals: respond colorimetrically to electrons. –Water: barrier to oxygen.

Required Conditions for Soil Reduction: –Exclusion of oxygen by water –Presence of organic matter – source of electrons –Microbial respiration – transfer of electrons –Electron acceptors How do Redoximorphic Features Form (cont.)?

How do Redoximorphic Features Form (Cont.)? Unsaturated -Oxygen is plentiful -Microbial respiration unrestricted Saturated -Oxygen is depleted -Microbes need alternative electron acceptors -Fe and Mn reduced and mobilized Unsaturated (drained) again -Oxygen re-enters -Fe and Mn oxidized and immobilized

Chemical reduction of Fe and Mn results in: -Loss of red, brown, yellow color (black for Mn). -Reduced soil zone becomes gray (unless blackened by OM). -Dissolution and potential mobilization. Re-oxidation results in: -Return of higher chroma color. -Immobilization. Cycles or zonal variations in redox result in: -Redistribution of Fe and Mn. -Patterns of color and consistence (morphological legacies). How do Redoximorphic Features Form (Cont.)? (another way to look at it …)

Broken soil ped (natural aggregate) Why is the ped interior red?

Review Drainage poor good ---- poor aeration, good aeration, reduced oxidized Fe 2+ + HCO ½ O 2 + H 2 O FeOOH + H 2 CO 3 soluble, mobile insoluble, residual gray orange, yellow, brown

D. Marl - secondary CaCO3 formation * CaCO3 indicates wet conditions in humid-region soils. - Carbonates would leach from well drained soils - Carbonates can form and remain stable in some wetlands - Near-sea-level limestone shelf of S. Florida is one example. Vertical movement of water is minimal. Lateral flow & evapotransporation prevalent. Underlying limestone provides Ca. Precipitation promoted by algal photosynthesis Ca (HCO 3 ) - = CaCO 3 + H 2 CO 3 H 2 O + CO 2

E. Near-surface stratification

F. Root Death Stripped Matrix