A redox gradient is a series of reduction-oxidation (

redox Redox ( , , reduction–oxidation or oxidation–reduction) is a type of chemical reaction in which the oxidation states of the reactants change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is t ...

) reactions sorted according to

redox potential Redox potential (also known as oxidation / reduction potential, ''ORP'', ''pe'', ''E_'', or E_) is a measure of the tendency of a chemical species to acquire electrons from or lose electrons to an electrode and thereby be reduced or oxidised respe ...

. The redox ladder displays the order in which redox reactions occur based on the free energy gained from redox pairs. These redox gradients form both spatially and temporally as a result of differences in microbial processes, chemical composition of the environment, and oxidative potential. Common environments where redox gradients exist are coastal marshes,

lake A lake is often a naturally occurring, relatively large and fixed body of water on or near the Earth's surface. It is localized in a basin or interconnected basins surrounded by dry land. Lakes lie completely on land and are separate from ...

s, contaminant plumes, and

soil Soil, also commonly referred to as earth, is a mixture of organic matter, minerals, gases, water, and organisms that together support the life of plants and soil organisms. Some scientific definitions distinguish dirt from ''soil'' by re ...

s. The

Earth Earth is the third planet from the Sun and the only astronomical object known to Planetary habitability, harbor life. This is enabled by Earth being an ocean world, the only one in the Solar System sustaining liquid surface water. Almost all ...

has a global redox gradient with an oxidizing environment at the surface and increasingly reducing conditions below the surface. 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.

Measuring redox conditions

Redox conditions are measured according to the redox potential (E_h) in volts, which represents the tendency for

electron The electron (, or in nuclear reactions) is a subatomic particle with a negative one elementary charge, elementary electric charge. It is a fundamental particle that comprises the ordinary matter that makes up the universe, along with up qua ...

s to transfer from an

electron donor In chemistry, an electron donor is a chemical entity that transfers electrons to another compound. It is a reducing agent that, by virtue of its donating electrons, is itself oxidized in the process. An obsolete definition equated an electron dono ...

to an

electron acceptor An electron acceptor is a chemical entity that accepts electrons transferred to it from another compound. Electron acceptors are oxidizing agents. The electron accepting power of an electron acceptor is measured by its redox potential. In the ...

. E_h can be calculated using half reactions and the

Nernst equation In electrochemistry, the Nernst equation is a chemical thermodynamical relationship that permits the calculation of the reduction potential of a reaction ( half-cell or full cell reaction) from the standard electrode potential, absolute tempera ...

. An E_h of zero represents the redox couple of the

standard hydrogen electrode In electrochemistry, the standard hydrogen electrode (abbreviated SHE), is a redox electrode which forms the basis of the thermodynamic scale of oxidation-reduction potentials. Its absolute electrode potential is estimated to be at 25 ° ...

H⁺/H_2, 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.

Environmental conditions

Redox gradients are commonly found in the environment as functions of both space and time, 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 A wetland is a distinct semi-aquatic ecosystem whose groundcovers are flooded or saturated in water, either permanently, for years or decades, or only seasonally. Flooding results in oxygen-poor ( anoxic) processes taking place, especially ...

, contaminant plumes, and marine

pelagic The pelagic zone consists of the water column of the open ocean and can be further divided into regions by depth. The word ''pelagic'' is derived . The pelagic zone can be thought of as an imaginary cylinder or water column between the sur ...

and

hemipelagic Hemipelagic sediment, or hemipelagite, is a type of marine sediment that consists of clay and silt-sized grains that are terrigenous and some biogenic material derived from the landmass nearest the deposits or from organisms living in the water. Hem ...

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): #

Aerobic respiration Cellular respiration is the process of oxidizing biological fuels using an inorganic electron acceptor, such as oxygen, to drive production of adenosine triphosphate (ATP), which stores chemical energy in a biologically accessible form. Cellu ...

(aerobes:

aerobic organisms An aerobic organism or aerobe is an organism that can survive and grow in an oxygenated environment. The ability to exhibit aerobic respiration may yield benefits to the aerobic organism, as aerobic respiration yields more energy than anaerobic ...

) #

Denitrification Denitrification is a microbially facilitated process where nitrate (NO3−) is reduced and ultimately produces molecular nitrogen (N2) through a series of intermediate gaseous nitrogen oxide products. Facultative anaerobic bacteria perform denitr ...

(denitrifiers:

denitrifying bacteria Denitrifying bacteria are a diverse group of bacteria that encompass many different phyla. This group of bacteria, together with denitrifying fungi and archaea, is capable of performing denitrification as part of the nitrogen cycle. Denitrification ...

) #

Manganese Manganese is a chemical element; it has Symbol (chemistry), symbol Mn and atomic number 25. It is a hard, brittle, silvery metal, often found in minerals in combination with iron. Manganese was first isolated in the 1770s. It is a transition m ...

reduction (Manganese reducers) #

Iron Iron is a chemical element; it has symbol Fe () and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, forming much of Earth's o ...

reduction (iron reducers: iron-reducing bacteria) #

Sulfate The sulfate or sulphate ion is a polyatomic anion with the empirical formula . Salts, acid derivatives, and peroxides of sulfate are widely used in industry. Sulfates occur widely in everyday life. Sulfates are salts of sulfuric acid and many ...

reduction (sulfate reducers:

Sulfur-reducing bacteria Sulfur-reducing bacteria are microorganisms able to reduce elemental sulfur (S0) to hydrogen sulfide (H2S). These microbes use inorganic sulfur compounds as electron acceptors to sustain several activities such as respiration, conserving energy a ...

) #

Methanogenesis Methanogenesis or biomethanation is the formation of methane coupled to energy conservation by microbes known as methanogens. It is the fourth and final stage of anaerobic digestion. Organisms capable of producing methane for energy conservation h ...

(

methanogens Methanogens are anaerobic archaea that produce methane as a byproduct of their energy metabolism, i.e., catabolism. Methane production, or methanogenesis, is the only biochemical pathway for ATP generation in methanogens. All known methanogens b ...

)

Aquatic environments

Redox gradients form in water columns and their sediments. Varying levels of oxygen (oxic, suboxic,

hypoxic Hypoxia means a lower than normal level of oxygen, and may refer to: Reduced or insufficient oxygen * Hypoxia (environmental), abnormally low oxygen content of a specific environment ** Hypoxia in fish, responses of fish to hypoxia * Hypoxia (medi ...

) within the water column alter redox chemistry and which redox reactions can occur. Development of

oxygen minimum zone The oxygen minimum zone (OMZ), sometimes referred to as the shadow zone, is the zone in which oxygen saturation in seawater in the ocean is at its lowest. This zone occurs at depths of about , depending on local circumstances. OMZs are found wor ...

s also contributes to formation of redox gradients.

Benthic The benthic zone is the ecological region at the lowest level of a body of water such as an ocean, lake, or stream, including the sediment surface and some sub-surface layers. The name comes from the Ancient Greek word (), meaning "the depths". ...

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.

Terrestrial environments

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

gleysol A gleysol or gley soil is a hydric soil that unless drained is saturated with groundwater for long enough to develop a characteristic colour pattern. The pattern is essentially made up of reddish, brownish, or yellowish colours at surfaces of so ...

s, while soils with gradients formed by stagnant water are classified as

stagnosol A Stagnosol in the World Reference Base for Soil Resources (WRB) is soil with strong mottling of the soil profile due to redox processes caused by stagnating surface water. Stagnosols are periodically wet and mottled in the topsoil and subso ...

s and

planosol A Planosol in the World Reference Base for Soil Resources is a soil with a light-coloured, coarse-textured, surface horizon that shows signs of periodic water stagnation and abruptly overlies a dense, slowly permeable subsoil with significantl ...

s. Soil ''E''_h generally ranges from −300 to +900 mV. The table below summarizes typical ''E''_h values for various soil conditions: 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, organic material or natural organic matter is the large source of carbon-based compounds found within natural and engineered, terrestrial, and aquatic environments. It is matter composed of organic compounds that have come fro ...

. Organic matter consumes oxygen as it decomposes, resulting in reducing soil conditions and lower E_h.

Role of microorganisms

Redox gradients form based on resource availability and physiochemical conditions (pH, salinity, temperature) and support stratified communities of

microbes A microorganism, or microbe, is an organism of microscopic size, which may exist in its single-celled form or as a colony of cells. The possible existence of unseen microbial life was suspected from antiquity, with an early attestation in ...

. Microbes carry out differing

respiration Respiration may refer to: Biology * Cellular respiration, the process in which nutrients are converted into useful energy in a cell ** Anaerobic respiration, cellular respiration without oxygen ** Maintenance respiration, the amount of cellul ...

processes (

methanogenesis Methanogenesis or biomethanation is the formation of methane coupled to energy conservation by microbes known as methanogens. It is the fourth and final stage of anaerobic digestion. Organisms capable of producing methane for energy conservation h ...

, 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 The capillary fringe is the subsurface layer in which groundwater seeps up from a water table by capillary action to fill pores. Pores at the base of the capillary fringe are filled with water due to tension saturation. This saturated portion of t ...

, 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.

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 Cable bacteria are filamentous bacteria that conduct electricity across distances over 1 cm in sediment and groundwater aquifers. Cable bacteria allow for long-distance electron transport, which connects electron donors to electron acceptors ...

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.

Biofilm A biofilm is a Syntrophy, syntrophic Microbial consortium, community of microorganisms in which cell (biology), cells cell adhesion, stick to each other and often also to a surface. These adherent cells become embedded within a slimy ext ...

s, found in

tidal flats Mudflats or mud flats, also known as tidal flats or, in Ireland, slob or slobs, are coastal wetlands that form in intertidal areas where sediments have been deposited by tides or rivers. A global analysis published in 2019 suggested that tidal ...

glacier A glacier (; or ) is a persistent body of dense ice, a form of rock, that is constantly moving downhill under its own weight. A glacier forms where the accumulation of snow exceeds its ablation over many years, often centuries. It acquires ...

hydrothermal vent Hydrothermal vents are fissures on the seabed from which geothermally heated water discharges. They are commonly found near volcanically active places, areas where tectonic plates are moving apart at mid-ocean ridges, ocean basins, and hot ...

s, and at the bottoms of aquatic environments, also exhibit redox gradients. The community of microbes—often metal- or

sulfate-reducing bacteria Sulfate-reducing microorganisms (SRM) or sulfate-reducing prokaryotes (SRP) are a group composed of sulfate-reducing bacteria (SRB) and sulfate-reducing archaea (SRA), both of which can perform anaerobic respiration utilizing sulfate () as termina ...

—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.

References