Redox gradient

Redox conditions are measured according to the redox potential (E_h) in volts, which represents the tendency for electrons to transfer from an electron donor to an electron acceptor. E_h can be calculated using half reactions and the Nernst equation. An E_h of zero represents the redox couple of the standard hydrogen electrode H⁺/H_2,{{Cite journal|last=Husson|first=Olivier|date=2013|title=Redox potential (Eh) and pH as drivers of soil/plant/microorganism systems: a transdisciplinary overview pointing to integrative opportunities for agronomy|journal=Plant and Soil|language=en|volume=362|issue=1–2|pages=389–417|doi=10.1007/s11104-012-1429-7|issn=0032-079X|s2cid=17059599|doi-access=free|bibcode=2013PlSoi.362..389H }} a positive E_h indicates an oxidizing environment (electrons will be accepted), and a negative E_h indicates a reducing environment (electrons will be donated). In a redox gradient, the most energetically favorable chemical reaction occurs at the "top" of the redox ladder and the least energetically favorable reaction occurs at the "bottom" of the ladder.

E_h can be measured by collecting samples in the field and performing analyses in the lab, or by inserting an electrode into the environment to collect in situ measurements. Typical environments to measure redox potential are in bodies of water, soils, and sediments, all of which can exhibit high levels of heterogeneity. Collecting a high number of samples can produce high spatial resolution, but at the cost of low temporal resolution since samples only reflect a singular a snapshot in time. In situ monitoring can provide high temporal resolution by collecting continuous real-time measurements, but low spatial resolution since the electrode is in a fixed location.

Redox properties can also be tracked with high spatial and temporal resolution through the use of induced-polarization imaging, however, further research is needed to fully understand contributions of redox species to polarization.

Redox gradients are commonly found in the environment as functions of both space and time,{{Cite journal|last=Vodyanitskii|first=Yu N.|date=2016|title=Biochemical processes in soil and groundwater contaminated by leachates from municipal landfills (Mini review)|journal=Annals of Agrarian Science|volume=14|issue=3|pages=249–256|doi=10.1016/j.aasci.2016.07.009|issn=1512-1887|doi-access=free|bibcode=2016AnAgS..14..249V }} particularly in soils and aquatic environments. Gradients are caused by varying physiochemical properties including availability of oxygen, soil hydrology, chemical species present, and microbial processes. Specific environments that are commonly characterized by redox gradients include waterlogged soils, wetlands, contaminant plumes, and marine pelagic and hemipelagic sediments.

The following is a list of common reactions that occur in the environment in order from oxidizing to reducing (organisms performing the reaction in parentheses):

1. Aerobic respiration (aerobes: aerobic organisms)
2. Denitrification (denitrifiers: denitrifying bacteria)
3. Manganese reduction (Manganese reducers)
4. Iron reduction (iron reducers: iron-reducing bacteria)
5. Sulfate reduction (sulfate reducers: Sulfur-reducing bacteria)
6. Methanogenesis (methanogens)

Redox gradients form in water columns and their sediments. Varying levels of oxygen (oxic, suboxic, hypoxic) within the water column alter redox chemistry and which redox reactions can occur.{{Cite journal|last1=Rue|first1=Eden L.|last2=Smith|first2=Geoffrey J.|last3=Cutter|first3=Gregory A.|last4=Bruland|first4=Kenneth W.|date=1997|title=The response of trace element redox couples to suboxic conditions in the water column|url=https://linkinghub.elsevier.com/retrieve/pii/S096706379600088X|journal=Deep Sea Research Part I: Oceanographic Research Papers|language=en|volume=44|issue=1|pages=113–134|doi=10.1016/S0967-0637(96)00088-X|bibcode=1997DSRI...44..113R |url-access=subscription}} Development of oxygen minimum zones also contributes to formation of redox gradients.

Benthic sediments exhibit redox gradients produced by variations in mineral composition, organic matter availability, structure, and sorption dynamics. Limited transport of dissolved electrons through subsurface sediments, combined with varying pore sizes of sediments creates significant heterogeneity in benthic sediments. Oxygen availability in sediments determines which microbial respiration pathways can occur, resulting in a vertical stratification of redox processes as oxygen availability decreases with depth.

Soil E_h is also largely a function of hydrological conditions. In the event of a flood, saturated soils can shift from oxic to anoxic, creating a reducing environment as anaerobic microbial processes dominate. Moreover, small anoxic hotspots may develop within soil pore spaces, creating reducing conditions. With time, the starting E_h of a soil can be restored as water drains and the soil dries out. Soils with redox gradients formed by ascending groundwater are classified as gleysols, while soils with gradients formed by stagnant water are classified as stagnosols and planosols.

Soil E_h generally ranges from −300 to +900 mV. The table below summarizes typical E_h values for various soil conditions:

class="wikitable" ! Soil conditions ! Typical Eh range (mV)

Waterlogged | Eh < +250

Aerated – moderately reduced | +100 < Eh < +400

Aerated – reduced | −100 < Eh < +100

Aerated – highly reduced | −300 < Eh < −100

Cultivated | +300 < Eh < +500

Generally accepted E_h limits that are tolerable by plants are +300 mV < E_h < +700 mV. 300 mV is the boundary value that separates aerobic from anaerobic conditions in wetland soils. Redox potential (E_h) is also closely tied to pH, and both have significant influence on the function of soil-plant-microorganism systems. The main source of electrons in soil is organic matter. Organic matter consumes oxygen as it decomposes, resulting in reducing soil conditions and lower E_h.

{{Gallery

|title=Examples of redox gradients in the environment

|width=100

|height=170

|align=center

|File:Soil wetland Morrow Mountain SP ncwetlands KG.jpg

|Wetland soils often experience redox gradients.

|alt1=A researcher's right hand holds out a thin metal sediment corer containing wetland soil from Morrow Mountain. The left hand holds out small bits of soil in the foreground of the image.

|File:Drivers of hypoxia and acidification in upwelling shelf systems.svg

|In productive ocean regions and enclosed basins, oxygen minimum zones and hypoxic zones may experience redox gradients in deep waters.

|alt2=Scientific schematic diagram of a continental shelf experiencing an oxygen minimum zone. The oxygen minimum zone is colored red. Arrows indicate processes such as upwelling, winds from the north, and seaward surface currents. Green dots indicate a phytoplankton bloom in surface waters.

|File:Checking wetland soil (7067589349).jpg

|In wetlands, organic-rich soils accumulate over time, and these soils often experience redox gradients.

|alt3=A researcher wearing a beige shirt and hat kneels in a wetland with tall grasses and pools of dark water. He is reaching into the soils of the wetland with one arm.

|File:Bama soil.png

|Some soils experience redox gradients.

|alt4=An image of a vertical slice of soil which has different colors in layers from light brown at the surface to red at depth.

|File:May 11, 2012 Sediment core from the McCormick and Baxter Superfund Site (7198638518).jpg

|Sediment cores like this one collected from estuaries, rivers, lakes, and bays often have redox gradients with depth down into the core.

|alt5=A diver's blue-gloved hands holds a cylindrical sediment core. The core is inside a plastic tube through which dark sediments and murky water can be seen. Image text reads "McCormick & Baxter Portland Harbor, OR Sediment Core Sampling". In the background there is the deck of a boat, water, a bridge, and a forested ridge.

|File: Normgley.jpg

|Gleysols or gley soils like this one in the Southern Black Forest in Germany often experience redox gradients.

|alt6=A red-and-white striped stick leans against a cut bank of soil. The soil has layers in colors from grey to brown and many plant roots. At the top of the image there are plants with large green leaves.

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Redox gradients form based on resource availability and physiochemical conditions (pH, salinity, temperature) and support stratified communities of microbes. Microbes carry out differing respiration processes (methanogenesis, sulfate reduction, etc.) based on the conditions around them and further amplify redox gradients present in the environment. However, distribution of microorganisms cannot solely be determined from thermodynamics (redox ladder), but is also influenced by ecological and physiological factors.

Redox gradients form along contaminant plumes, in both aquatic and terrestrial settings, as a function of the contaminant concentration and the impacts it has on relevant chemical processes and microbial communities. The highest rates of organic pollutant degradation along a redox gradient are found at the oxic-anoxic interface. In groundwater, this oxic-anoxic environment is referred to as the capillary fringe, where the water table meets soil and fills empty pores. Because this transition zone is both oxic and anoxic, electron acceptors and donors are in high abundance and there is a high level of microbial activity, leading to the highest rates of contaminant biodegradation.

Benthic sediments are heterogeneous in nature and subsequently exhibit redox gradients. Due to this heterogeneity, gradients of reducing and oxidizing chemical species do not always overlap enough to support electron transport needs of niche microbial communities. Cable bacteria have been characterized as sulfide-oxidizing bacteria that assist in connecting these areas of undersupplied and excess electrons to complete the electron transport for otherwise unavailable redox reactions.

Biofilms, found in tidal flats, glaciers, hydrothermal vents, and at the bottoms of aquatic environments, also exhibit redox gradients. The community of microbes—often metal- or sulfate-reducing bacteria—produces redox gradients on the micrometer scale as a function of spatial physiochemical variability.

See sulfate-methane transition zone for coverage of microbial processes in SMTZs.

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• Anaerobic respiration
• Chemocline
• Gibbs free energy
• Dead zone (ecology)
• Hypoxia (environmental)
• Marine sediment
• Redox
• Redox potential
• Remineralization
• Sediment-water interface
• Sulfate-methane transition zone

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