Total inorganic carbon

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Total inorganic carbon (CT or TIC) is the sum of the inorganic carbon species.

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Carbon compounds can be distinguished as either organic or inorganic, and dissolved or particulate, depending on their composition. Organic carbon forms the backbone of key components of organic compounds such as proteins, lipids, carbohydrates, and nucleic acids. Inorganic carbon is found primarily in simple compounds such as carbon dioxide (CO2), carbonic acid (H2CO3), bicarbonate (HCO−3), and carbonate (CO2−3).

Overview

The aquatic inorganic carbon system is composed of the various ionic, dissolved, solid, and/or gaseous forms of carbon dioxide in water. These species include dissolved carbon dioxide, carbonic acid, bicarbonate anion, carbonate anion, calcium carbonate, magnesium carbonate, and others. The relative amounts of each species in a body of water depends on physical variables including temperature and salinity, as well as chemical variables like pH and gas partial pressure. Variables like alkalinity and dissolved (or total) inorganic carbon further define a mass and charge balance that constrains the total state of the system. [1] [2]

Given any two of the four central inorganic carbon system parameters (pH, alkalinity, dissolved inorganic carbon, partial pressure of carbon dioxide) the remainder may be derived by solving a system of equations that adhere to the principles of chemical thermodynamics. [2]

For most of the 20th century, chemical equilibria in marine and freshwater systems was calculated according to various conventions, which led to discrepancies among laboratories' calculations and limited scientific reproducibility. [3] Since 1998, a family of software programs called CO2SYS has been widely used. This software calculate chemical equilibria for aquatic inorganic carbon species and parameters. Their core function is to use any two of the four central inorganic carbon system parameters (pH, alkalinity, dissolved inorganic carbon, and partial pressure of carbon dioxide) to calculate various chemical properties of the system. The programs are widely used by oceanographers and limnologists to understand and predict chemical equilibria in natural waters. [4]

Inorganic carbon species

Carbon is separated into four distinct pools based on whether it is organic or inorganic, and whether it is dissolved or particulate. The processes associated with each arrow describe the transformation associated with the transfer of carbon from one reservoir to another. Marine carbon cycle.png
Carbon is separated into four distinct pools based on whether it is organic or inorganic, and whether it is dissolved or particulate. The processes associated with each arrow describe the transformation associated with the transfer of carbon from one reservoir to another.

The inorganic carbon species include carbon dioxide, carbonic acid, bicarbonate anion, and carbonate. [5] It is customary to express carbon dioxide and carbonic acid simultaneously as CO2*. CT is a key parameter when making measurements related to the pH of natural aqueous systems, [6] and carbon dioxide flux estimates.

where,

Each of these species are related by the following pH-driven chemical equilibria:

The concentrations of the different species of DIC (and which species is dominant) depends on the pH of the solution, as shown by a Bjerrum plot.

Total inorganic carbon is typically measured by the acidification of the sample which drives the equilibria to CO2. This gas is then sparged from solution and trapped, and the quantity trapped is then measured, usually by infrared spectroscopy.

Marine carbon

Relationship between carbon types Total Carbon (TC).svg
Relationship between carbon types

Marine carbon is further separated into particulate and dissolved phases. These pools are operationally defined by physical separation – dissolved carbon passes through a 0.2 μm filter, and particulate carbon does not.

There are two main types of inorganic carbon that are found in the oceans:

Some of the inorganic carbon species in the ocean, such as bicarbonate and carbonate, are major contributors to alkalinity, a natural ocean buffer that prevents drastic changes in acidity (or pH). The marine carbon cycle also affects the reaction and dissolution rates of some chemical compounds, regulates the amount of carbon dioxide in the atmosphere and Earth's temperature. [8]

Related Research Articles

<span class="mw-page-title-main">Bicarbonate</span> Polyatomic anion

In inorganic chemistry, bicarbonate is an intermediate form in the deprotonation of carbonic acid. It is a polyatomic anion with the chemical formula HCO−
3.

<span class="mw-page-title-main">Carbon dioxide</span> Chemical compound with formula CO2

Carbon dioxide is a chemical compound with the chemical formula CO2. It is made up of molecules that each have one carbon atom covalently double bonded to two oxygen atoms. It is found in the gas state at room temperature, and as the source of available carbon in the carbon cycle, atmospheric CO2 is the primary carbon source for life on Earth. In the air, carbon dioxide is transparent to visible light but absorbs infrared radiation, acting as a greenhouse gas. Carbon dioxide is soluble in water and is found in groundwater, lakes, ice caps, and seawater. When carbon dioxide dissolves in water, it forms carbonate and mainly bicarbonate, which causes ocean acidification as atmospheric CO2 levels increase.

<span class="mw-page-title-main">Carbonate</span> Salt of carbonic acid

A carbonate is a salt of carbonic acid (H2CO3), characterized by the presence of the carbonate ion, a polyatomic ion with the formula CO2−3. The word carbonate may also refer to a carbonate ester, an organic compound containing the carbonate groupO=C(−O−)2.

<span class="mw-page-title-main">Calcium carbonate</span> Chemical compound

Calcium carbonate is a chemical compound with the chemical formula CaCO3. It is a common substance found in rocks as the minerals calcite and aragonite, most notably in chalk and limestone, eggshells, gastropod shells, shellfish skeletons and pearls. Materials containing much calcium carbonate or resembling it are described as calcareous. Calcium carbonate is the active ingredient in agricultural lime and is produced when calcium ions in hard water react with carbonate ions to form limescale. It has medical use as a calcium supplement or as an antacid, but excessive consumption can be hazardous and cause hypercalcemia and digestive issues.

In chemistry, carbonic acid is an organic compound with the chemical formula H2CO3. The molecule rapidly converts to water and carbon dioxide in the presence of water. However, in the absence of water, it is quite stable at room temperature. The interconversion of carbon dioxide and carbonic acid is related to the breathing cycle of animals and the acidification of natural waters.

<span class="mw-page-title-main">Biological pump</span> Carbon capture process in oceans

The biological pump (or ocean carbon biological pump or marine biological carbon pump) is the ocean's biologically driven sequestration of carbon from the atmosphere and land runoff to the ocean interior and seafloor sediments. In other words, it is a biologically mediated process which results in the sequestering of carbon in the deep ocean away from the atmosphere and the land. The biological pump is the biological component of the "marine carbon pump" which contains both a physical and biological component. It is the part of the broader oceanic carbon cycle responsible for the cycling of organic matter formed mainly by phytoplankton during photosynthesis (soft-tissue pump), as well as the cycling of calcium carbonate (CaCO3) formed into shells by certain organisms such as plankton and mollusks (carbonate pump).

A hydrogen ion is created when a hydrogen atom loses an electron. A positively charged hydrogen ion (or proton) can readily combine with other particles and therefore is only seen isolated when it is in a gaseous state or a nearly particle-free space. Due to its extremely high charge density of approximately 2×1010 times that of a sodium ion, the bare hydrogen ion cannot exist freely in solution as it readily hydrates, i.e., bonds quickly. The hydrogen ion is recommended by IUPAC as a general term for all ions of hydrogen and its isotopes. Depending on the charge of the ion, two different classes can be distinguished: positively charged ions and negatively charged ions.

<span class="mw-page-title-main">Alkalinity</span> Capacity of water to resist changes in pH that would make the water more acidic

Alkalinity (from Arabic: القلوية, romanized: al-qaly, lit. 'ashes of the saltwort') is the capacity of water to resist acidification. It should not be confused with basicity, which is an absolute measurement on the pH scale. Alkalinity is the strength of a buffer solution composed of weak acids and their conjugate bases. It is measured by titrating the solution with an acid such as HCl until its pH changes abruptly, or it reaches a known endpoint where that happens. Alkalinity is expressed in units of concentration, such as meq/L (milliequivalents per liter), μeq/kg (microequivalents per kilogram), or mg/L CaCO3 (milligrams per liter of calcium carbonate). Each of these measurements corresponds to an amount of acid added as a titrant.

<span class="mw-page-title-main">Solubility pump</span> Physico-chemical process which transports carbon

In oceanic biogeochemistry, the solubility pump is a physico-chemical process that transports carbon as dissolved inorganic carbon (DIC) from the ocean's surface to its interior.

Calcium bicarbonate, also called calcium hydrogencarbonate, has the chemical formula Ca(HCO3)2. The term does not refer to a known solid compound; it exists only in aqueous solution containing calcium (Ca2+), bicarbonate (HCO−
3), and carbonate (CO2−
3) ions, together with dissolved carbon dioxide (CO2). The relative concentrations of these carbon-containing species depend on the pH; bicarbonate predominates within the range 6.36–10.25 in fresh water.

<span class="mw-page-title-main">Dissolved inorganic carbon</span> Sum of inorganic carbon species in a solution

Dissolved inorganic carbon (DIC) is the sum of the aqueous species of inorganic carbon in a solution. Carbon compounds can be distinguished as either organic or inorganic, and as dissolved or particulate, depending on their composition. Organic carbon forms the backbone of key component of organic compounds such as – proteins, lipids, carbohydrates, and nucleic acids.

<span class="mw-page-title-main">Alkali soil</span> Soil type with pH > 8.5

Alkali, or Alkaline, soils are clay soils with high pH, a poor soil structure and a low infiltration capacity. Often they have a hard calcareous layer at 0.5 to 1 metre depth. Alkali soils owe their unfavorable physico-chemical properties mainly to the dominating presence of sodium carbonate, which causes the soil to swell and difficult to clarify/settle. They derive their name from the alkali metal group of elements, to which sodium belongs, and which can induce basicity. Sometimes these soils are also referred to as alkaline sodic soils.
Alkaline soils are basic, but not all basic soils are alkaline.

<span class="mw-page-title-main">Acid neutralizing capacity</span> Measure for the overall buffering capacity against acidification of a solution

Acid-neutralizing capacity or ANC in short is a measure for the overall buffering capacity against acidification of a solution, e.g. surface water or soil water.

<span class="mw-page-title-main">Carbonate–silicate cycle</span> Geochemical transformation of silicate rocks

The carbonate–silicate geochemical cycle, also known as the inorganic carbon cycle, describes the long-term transformation of silicate rocks to carbonate rocks by weathering and sedimentation, and the transformation of carbonate rocks back into silicate rocks by metamorphism and volcanism. Carbon dioxide is removed from the atmosphere during burial of weathered minerals and returned to the atmosphere through volcanism. On million-year time scales, the carbonate-silicate cycle is a key factor in controlling Earth's climate because it regulates carbon dioxide levels and therefore global temperature.

<span class="mw-page-title-main">Bjerrum plot</span> Graph of polyprotic acid concentration compared to pH

A Bjerrum plot (named after Niels Bjerrum), sometimes also known as a Sillén diagram (after Lars Gunnar Sillén), or a Hägg diagram (after Gunnar Hägg) is a graph of the concentrations of the different species of a polyprotic acid in a solution, as a function of pH, when the solution is at equilibrium. Due to the many orders of magnitude spanned by the concentrations, they are commonly plotted on a logarithmic scale. Sometimes the ratios of the concentrations are plotted rather than the actual concentrations. Occasionally H+ and OH− are also plotted.

The Revelle factor (buffer factor) is the ratio of instantaneous change in carbon dioxide (CO2) to the change in total dissolved inorganic carbon (DIC), and is a measure of the resistance to atmospheric CO2 being absorbed by the ocean surface layer. The buffer factor is used to examine the distribution of CO2 between the atmosphere and the ocean, and measures the amount of CO2 that can be dissolved in the mixed surface layer. It is named after the oceanographer Roger Revelle. The Revelle factor describes the ocean's ability to uptake atmospheric CO2, and is typically referenced in global carbon budget analysis and anthropogenic climate change studies.

<span class="mw-page-title-main">Oceanic carbon cycle</span> Ocean/atmosphere carbon exchange process

The oceanic carbon cycle is composed of processes that exchange carbon between various pools within the ocean as well as between the atmosphere, Earth interior, and the seafloor. The carbon cycle is a result of many interacting forces across multiple time and space scales that circulates carbon around the planet, ensuring that carbon is available globally. The Oceanic carbon cycle is a central process to the global carbon cycle and contains both inorganic carbon and organic carbon. Part of the marine carbon cycle transforms carbon between non-living and living matter.

<span class="mw-page-title-main">Freshwater acidification</span>

Freshwater acidification occurs when acidic inputs enter a body of fresh water through the weathering of rocks, invasion of acidifying gas, or by the reduction of acid anions, like sulfate and nitrate within a lake. Freshwater acidification is primarily caused by sulfur oxides (SOx) and nitrogen oxides (NOx) entering the water from atmospheric depositions and soil leaching. Carbonic acid and dissolved carbon dioxide can also enter freshwaters, in a similar manner associated with runoff, through carbon dioxide-rich soils. Runoff that contains these compounds may incorporate acidifying hydrogen ions and inorganic aluminum, which can be toxic to marine organisms. Acid rain is also a contributor to freshwater acidification. It is created when SOx and NOx react with water, oxygen, and other oxidants within the clouds.

CO2SYS is a family of software programs that calculate chemical equilibria for aquatic inorganic carbon species and parameters. Their core function is to use any two of the four central inorganic carbon system parameters to calculate various chemical properties of the system. These programs are widely used by oceanographers and limnologists to understand and predict chemical equilibria in natural waters.

<span class="mw-page-title-main">Particulate inorganic carbon</span>

Particulate inorganic carbon (PIC) can be contrasted with dissolved inorganic carbon (DIC), the other form of inorganic carbon found in the ocean. These distinctions are important in chemical oceanography. Particulate inorganic carbon is sometimes called suspended inorganic carbon. In operational terms, it is defined as the inorganic carbon in particulate form that is too large to pass through the filter used to separate dissolved inorganic carbon.

References

  1. ↑ Zeebe, Richard E.; Wolf-Gladrow, Dieter A. (15 October 2001). CO2 in Seawater: Equilibrium, Kinetics, Isotopes. Amsterdam. ISBN   978-0-08-052922-6. OCLC   246683387.{{cite book}}: CS1 maint: location missing publisher (link)
  2. 1 2 Stumm, Werner; Morgan, James J. (2012). Aquatic Chemistry: Chemical Equilibria and Rates in Natural Waters (3rd ed.). Hoboken: Wiley. ISBN   978-1-118-59148-2. OCLC   830169758.
  3. ↑ Lewis; Wallace (1998). "Program Developed for CO2 System Calculations". ORNL/CDIAC-105.
  4. ↑ Orr, J. C.; Epitalon, J.-M.; Gattuso, J.-P. (2015-03-09). "Comparison of ten packages that compute ocean carbonate chemistry". Biogeosciences. 12 (5): 1483–1510. Bibcode:2015BGeo...12.1483O. doi: 10.5194/bg-12-1483-2015 . ISSN   1726-4189.
  5. ↑ C. Michael Hogan. 2010. Calcium. eds. A. Jorgensen, C. Cleveland. Encyclopedia of Earth. National Council for Science and the Environment.
  6. ↑ Stanley E. Manahan. 2005. Environmental chemistry. CRC Press
  7. ↑ Wilson, R. W.; Millero, F. J.; Taylor, J. R.; Walsh, P. J.; Christensen, V.; Jennings, S.; Grosell, M. (2009-01-16). "Contribution of Fish to the Marine Inorganic Carbon Cycle". Science. 323 (5912): 359–362. Bibcode:2009Sci...323..359W. doi:10.1126/science.1157972. ISSN   0036-8075. PMID   19150840. S2CID   36321414.
  8. ↑ Emerson, Steven (2008). Chemical Oceanography and the Marine Carbon Cycle. United Kingdom: Cambridge University Press. ISBN   978-0-521-83313-4.
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