{{Short description|Variation of the redox potential with distance (or depth)}} {{Broader|Redox|Reduction potential}} thumb|Depiction of common redox reactions in the environment. Adapted from figures by Zhang<ref name=":0">{{Cite journal|last1=Zhang|first1=Zengyu|last2=Furman|first2=Alex|date=2021|title=Soil redox dynamics under dynamic hydrologic regimes - A review|url=https://www.sciencedirect.com/science/article/pii/S0048969720365566|journal=Science of the Total Environment|language=en|volume=763|article-number=143026|bibcode=2021ScTEn.76343026Z|doi=10.1016/j.scitotenv.2020.143026|issn=0048-9697|pmid=33143917|s2cid=226249448|url-access=subscription}}</ref> and Gorny.<ref>{{Cite journal|last1=Gorny|first1=J.|last2=Billon|first2=G.|last3=Lesven|first3=L.|last4=Dumoulin|first4=D.|last5=Madé|first5=B.|last6=Noiriel|first6=C.|date=2015|title=Arsenic behavior in river sediments under redox gradient: a review.|journal=The Science of the Total Environment|volume=505|pages=423–434|doi=10.1016/j.scitotenv.2014.10.011|pmid=25461044|s2cid=24877798}}</ref> Redox pairs are listed with the oxidizer (electron acceptor) in red and the reducer (electron donator) in black. thumb|Relative favorability of redox reactions in marine sediments based on energy. Start points of arrows indicate energy associated with half-cell reaction. Lengths of arrows indicate an estimate of Gibb's free energy (ΔG) for the reaction where a higher ΔG is more energetically favorable (Adapted from Libes, 2011).<ref name="Libes2">{{cite book|last=Libes|first=Susan|title=Introduction to marine biogeochemistry|publisher=Elsevier/Academic Press|year=2009|isbn=978-0-08-091664-4|publication-place=Amsterdam Boston|page=|oclc=643573176}}</ref> A '''redox gradient''' is a series of reduction-oxidation (redox) reactions sorted according to redox potential.<ref name="Borch Kretzschmar Kappler Cappellen pp. 15–232">{{cite journal|last1=Borch|first1=Thomas|last2=Kretzschmar|first2=Ruben|last3=Kappler|first3=Andreas|last4=Cappellen|first4=Philippe Van|last5=Ginder-Vogel|first5=Matthew|last6=Voegelin|first6=Andreas|last7=Campbell|first7=Kate|date=2009|title=Biogeochemical Redox Processes and their Impact on Contaminant Dynamics|journal=Environmental Science & Technology|publisher=American Chemical Society (ACS)|volume=44|issue=1|pages=15–23|doi=10.1021/es9026248|issn=0013-936X|pmid=20000681|s2cid=206997593 |url=https://www.dora.lib4ri.ch/eawag/islandora/object/eawag%3A6270 |url-access=subscription}}</ref><ref name=":3">{{Cite journal|last1=Lau|first1=Maximilian Peter|last2=Niederdorfer|first2=Robert|last3=Sepulveda-Jauregui|first3=Armando|last4=Hupfer|first4=Michael|date=2018|title=Synthesizing redox biogeochemistry at aquatic interfaces|journal=Limnologica|language=en|volume=68|pages=59–70|doi=10.1016/j.limno.2017.08.001|doi-access=free|bibcode=2018Limng..68...59L }}</ref> The redox ladder displays the order in which redox reactions occur based on the free energy gained from redox pairs.<ref name="Borch Kretzschmar Kappler Cappellen pp. 15–232" /><ref name=":3" /><ref name=":5">{{Cite journal|last1=Peiffer|first1=S.|last2=Kappler|first2=A.|last3=Haderlein|first3=S. B.|last4=Schmidt|first4=C.|last5=Byrne|first5=J. M.|last6=Kleindienst|first6=S.|last7=Vogt|first7=C.|last8=Richnow|first8=H. H.|last9=Obst|first9=M.|last10=Angenent|first10=L. T.|last11=Bryce|first11=C.|date=2021|title=A biogeochemical–hydrological framework for the role of redox-active compounds in aquatic systems|url=http://www.nature.com/articles/s41561-021-00742-z|journal=Nature Geoscience|language=en|volume=14|issue=5|pages=264–272|doi=10.1038/s41561-021-00742-z|bibcode=2021NatGe..14..264P |s2cid=233876038 |issn=1752-0894|url-access=subscription}}</ref> These redox gradients form both spatially and temporally as a result of differences in microbial processes, chemical composition of the environment, and oxidative potential.<ref name=":3" /><ref name="Borch Kretzschmar Kappler Cappellen pp. 15–232" /> Common environments where redox gradients exist are coastal marshes, lakes, contaminant plumes, and soils.<ref name=":0" /><ref name="Borch Kretzschmar Kappler Cappellen pp. 15–232" /><ref name=":3" /><ref name=":5" />
The Earth has a global redox gradient with an oxidizing environment at the surface and increasingly reducing conditions below the surface.<ref name="Borch Kretzschmar Kappler Cappellen pp. 15–232" /> Redox gradients are generally understood at the macro level, but characterization of redox reactions in heterogeneous environments at the micro-scale require further research and more sophisticated measurement techniques.<ref name=":3" /><ref name=":0" /><ref name=":4">{{Cite journal|last1=Zakem|first1=Emily J.|last2=Polz|first2=Martin F.|last3=Follows|first3=Michael J.|date=2020|title=Redox-informed models of global biogeochemical cycles|journal=Nature Communications|language=en|volume=11|issue=1|page=5680|doi=10.1038/s41467-020-19454-w|pmid=33173062 |pmc=7656242 |bibcode=2020NatCo..11.5680Z |issn=2041-1723}}</ref><ref name=":5" />
== Measuring redox conditions == Redox conditions are measured according to the redox potential (E<sub>h</sub>) in volts, which represents the tendency for electrons to transfer from an electron donor to an electron acceptor. E<sub>h</sub> can be calculated using half reactions and the Nernst equation.<ref name=":0" /> An E<sub>h</sub> of zero represents the redox couple of the standard hydrogen electrode H<sup>+</sup>/H<sub>2,</sub><ref name=":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 }}</ref> a positive E<sub>h</sub> indicates an oxidizing environment (electrons will be accepted), and a negative E<sub>h</sub> indicates a reducing environment (electrons will be donated).<ref name=":0" /> 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.<ref name=":0" />
E<sub>h</sub> 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.<ref name=":5" /><ref name=":3" /><ref name=":0" /> Typical environments to measure redox potential are in bodies of water, soils, and sediments, all of which can exhibit high levels of heterogeneity.<ref name=":3" /><ref name=":0" /> 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.<ref name=":2" /><ref name=":0" /><ref name=":3" /> 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.<ref name=":0" /><ref name=":3" />
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.<ref name=":5" />
== Environmental conditions == Redox gradients are commonly found in the environment as functions of both space and time,<ref name=":1">{{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 }}</ref><ref name=":2" /> particularly in soils and aquatic environments.<ref name=":2" /><ref name=":5" /> Gradients are caused by varying physiochemical properties including availability of oxygen, soil hydrology, chemical species present, and microbial processes.<ref name=":0" /><ref name="Borch Kretzschmar Kappler Cappellen pp. 15–232" /><ref name=":1" /><ref name=":2" /> Specific environments that are commonly characterized by redox gradients include waterlogged soils, wetlands,<ref name=":2" /> contaminant plumes,<ref name=":1" /><ref name="Borch Kretzschmar Kappler Cappellen pp. 15–232" /> and marine pelagic and hemipelagic sediments.<ref name="Borch Kretzschmar Kappler Cappellen pp. 15–232" />
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):<ref name=":0" />
# Aerobic respiration (aerobes: aerobic organisms) # Denitrification (denitrifiers: denitrifying bacteria) # Manganese reduction (Manganese reducers) # Iron reduction (iron reducers: iron-reducing bacteria) # Sulfate reduction (sulfate reducers: Sulfur-reducing bacteria) # Methanogenesis (methanogens)
=== Aquatic environments === 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.<ref>{{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}}</ref> 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.<ref name=":3" /> Limited transport of dissolved electrons through subsurface sediments, combined with varying pore sizes of sediments creates significant heterogeneity in benthic sediments.<ref name=":3" /> 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.<ref name=":3" />
=== Terrestrial environments === Soil ''E''<sub>h</sub> is also largely a function of hydrological conditions.<ref name=":0" /><ref name=":2" /><ref name=":5" /> In the event of a flood, saturated soils can shift from oxic to anoxic, creating a reducing environment as anaerobic microbial processes dominate.<ref name=":0" /><ref name=":2" /> Moreover, small anoxic hotspots may develop within soil pore spaces, creating reducing conditions.<ref name=":5" /> With time, the starting ''E''<sub>h</sub> of a soil can be restored as water drains and the soil dries out.<ref name=":0" /><ref name=":2" /> 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''<sub>h</sub> generally ranges from −300 to +900 mV.<ref name=":2" /> The table below summarizes typical ''E''<sub>h</sub> values for various soil conditions:<ref name=":0" /><ref name=":2" /> {| class="wikitable" ! Soil conditions ! Typical ''E''<sub>h</sub> range (mV)<ref name=":0" /><ref name=":2" /> |- | Waterlogged | ''E''<sub>h</sub> < +250 |- | Aerated – moderately reduced | +100 < ''E''<sub>h</sub> < +400 |- | Aerated – reduced | −100 < ''E''<sub>h</sub> < +100 |- | Aerated – highly reduced | −300 < ''E''<sub>h</sub> < −100 |- | Cultivated | +300 < ''E''<sub>h</sub> < +500 |} Generally accepted ''E''<sub>h</sub> limits that are tolerable by plants are +300 mV < ''E''<sub>h</sub> < +700 mV.<ref name=":2" /> 300 mV is the boundary value that separates aerobic from anaerobic conditions in wetland soils.<ref name=":0" /> Redox potential (E<sub>h</sub>) is also closely tied to pH, and both have significant influence on the function of soil-plant-microorganism systems.<ref name=":0" /><ref name=":2" /> The main source of electrons in soil is organic matter.<ref name=":2" /> Organic matter consumes oxygen as it decomposes, resulting in reducing soil conditions and lower E<sub>h</sub>.<ref name=":2" />
{{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. }}
== Role of microorganisms == Redox gradients form based on resource availability and physiochemical conditions (pH, salinity, temperature) and support stratified communities of microbes.<ref name=":0" /><ref name=":3" /><ref name=":1" /><ref name=":2" /><ref name=":4" /> 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.<ref name=":1" /><ref name=":0" /><ref name=":2" /> However, distribution of microorganisms cannot solely be determined from thermodynamics (redox ladder), but is also influenced by ecological and physiological factors.<ref name=":5" /><ref name=":3" />
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.<ref name=":0" /><ref name=":1" /> The highest rates of organic pollutant degradation along a redox gradient are found at the oxic-anoxic interface.<ref name=":0" /> 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.<ref name=":0" /><ref name=":1" />
Benthic sediments are heterogeneous in nature and subsequently exhibit redox gradients.<ref name=":3" /> 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.<ref name=":3" /> 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.<ref name=":3" />
Biofilms, found in tidal flats, glaciers, hydrothermal vents, and at the bottoms of aquatic environments, also exhibit redox gradients.<ref name=":3" /> The community of microbes—often metal- or sulfate-reducing bacteria—produces redox gradients on the micrometer scale as a function of spatial physiochemical variability.<ref name=":3" />
See sulfate-methane transition zone for coverage of microbial processes in SMTZs.
== See also == {{Portal|Environment|Chemistry|Oceans }} * Anaerobic respiration * Chemocline * Gibbs free energy * Dead zone (ecology) * Hypoxia (environmental) * Marine sediment * Redox * Redox potential * Remineralization * Sediment-water interface * Sulfate-methane transition zone
==References== {{Reflist}}
Category:Aquatic ecology Category:Biogeochemistry Category:Chemical oceanography Category:Electrochemistry Category:Environmental chemistry Category:Environmental science Category:Limnology Category:Marine geology Category:Oceanographical terminology Category:Oceanography Category:Redox Category:Sediments Category:Soil science