A redox gradient is a series of reduction-oxidation (

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

) 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 an area filled with water, localized in a basin, surrounded by land, and distinct from any river or other outlet that serves to feed or drain the lake. Lakes lie on land and are not part of the ocean, although, like the much large ...

s, contaminant plumes, and

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

s. The

Earth Earth is the third planet from the Sun and the only astronomical object known to harbor life. While large volumes of water can be found throughout the Solar System, only Earth sustains liquid surface water. About 71% of Earth's surfa ...

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 ) is a subatomic particle with a negative one elementary electric charge. Electrons belong to the first generation of the lepton particle family, and are generally thought to be elementary particles because they have no kn ...

s to transfer from an

electron donor In chemistry, an electron donor is a chemical entity that donates electrons to another compound. It is a reducing agent that, by virtue of its donating electrons, is itself oxidized in the process. Typical reducing agents undergo permanent chem ...

to an

electron acceptor An electron acceptor is a chemical entity that accepts electrons transferred to it from another compound. It is an oxidizing agent that, by virtue of its accepting electrons, is itself reduced in the process. Electron acceptors are sometimes mista ...

. E_h can be calculated using half reactions and the

Nernst equation In electrochemistry, the Nernst equation is a Thermodynamics#Chemical thermodynamics, chemical thermodynamical relationship that permits the calculation of the reduction potential of a reaction (half-cell or electrochemical cell, full cell reacti ...

. An E_h of zero represents the redox couple of the

standard hydrogen electrode 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 °C, but to form a basis f ...

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 ecosystem that is flooded or saturated by water, either permanently (for years or decades) or seasonally (for weeks or months). Flooding results in oxygen-free (anoxic) processes prevailing, especially in the soils. The ...

, 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 (as illustrated on the right). The word ''pelagic'' is derived . The pelagic zone can be thought of as an imaginary cylinder or wa ...

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. He ...

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 by which biological fuels are oxidised in the presence of an inorganic electron acceptor such as oxygen to produce large amounts of energy, to drive the bulk production of ATP. Cellular respiration may be des ...

(aerobes:

aerobic organisms Aerobic means "requiring air," in which "air" usually means oxygen. Aerobic may also refer to * Aerobic exercise, prolonged exercise of moderate intensity * Aerobics, a form of aerobic exercise * Aerobic respiration, the aerobic process of cellu ...

) #

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 with the symbol Mn and atomic number 25. It is a hard, brittle, silvery metal, often found in minerals in combination with iron. Manganese is a transition metal with a multifaceted array of industrial alloy use ...

reduction (Manganese reducers) #

Iron Iron () is a chemical element with symbol Fe (from la, ferrum) 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, right in f ...

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 ar ...

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 an ...

) #

Methanogenesis Methanogenesis or biomethanation is the formation of methane coupled to energy conservation by microbes known as methanogens. Organisms capable of producing methane for energy conservation have been identified only from the domain Archaea, a group ...

(

methanogens Methanogens are microorganisms that produce methane as a metabolic byproduct in hypoxic conditions. They are prokaryotic and belong to the domain Archaea. All known methanogens are members of the archaeal phylum Euryarchaeota. Methanogens are comm ...

)

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 the specific environment * Hypoxia (medical), abnormally low level of oxygen in the tis ...

) 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 worl ...

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 ancient Greek, βένθος (bénthos), meaning "t ...

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 is a wetland soil (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 o ...

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 subsoil, w ...

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 significantly ...

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 refers to 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 c ...

. 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,, ''mikros'', "small") and ''organism'' from the el, ὀργανισμός, ''organismós'', "organism"). It is usually written as a single word but is sometimes hyphenated (''micro-organism''), especially in olde ...

. 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 cellula ...

processes (

methanogenesis Methanogenesis or biomethanation is the formation of methane coupled to energy conservation by microbes known as methanogens. Organisms capable of producing methane for energy conservation have been identified only from the domain Archaea, a group ...

, 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 acceptor ...

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 comprises any syntrophic consortium of microorganisms in which cells stick to each other and often also to a surface. These adherent cells become embedded within a slimy extracellular matrix that is composed of extracellular ...

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 fl ...

glacier A glacier (; ) is a persistent body of dense ice that is constantly moving under its own weight. A glacier forms where the accumulation of snow exceeds its Ablation#Glaciology, ablation over many years, often Century, centuries. It acquires dis ...

hydrothermal vent A hydrothermal vent is a fissure 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 hotspot ...

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 The sulfate-methane transition zone (SMTZ) is a zone in oceans, lakes, and rivers found below the sediment surface in which sulfate and methane coexist. The formation of a SMTZ is driven by the diffusion of sulfate down the sediment column and the d ...

for coverage of microbial processes in SMTZs.

References