Chemistry:Carbon-to-nitrogen ratio

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A carbon-to-nitrogen ratio (C/N ratio or C:N ratio) is a ratio of the mass of carbon to the mass of nitrogen in organic residues. It can, amongst other things, be used in analysing sediments and soil including soil organic matter and soil amendments such as compost.

Sediments

In the analysis of sediments, C/N ratios are a proxy for paleoclimate research, having different uses whether the sediment cores are terrestrial-based or marine-based. Carbon-to-nitrogen ratios are an indicator for nitrogen limitation of plants and other organisms and can identify whether molecules found in the sediment under study come from land-based or algal plants.[1] Further, they can distinguish between different land-based plants, depending on the type of photosynthesis they undergo. Therefore, the C/N ratio serves as a tool for understanding the sources of sedimentary organic matter, which can lead to information about the ecology, climate, and ocean circulation at different times in Earth's history.[1]

Ranges

C/N ratios in the range 4-10:1 are usually from marine sources, whereas higher ratios are likely to come from a terrestrial source.[2][3] Vascular plants from terrestrial sources tend to have C/N ratios greater than 20.[1][4] The lack of cellulose, which has a chemical formula of (C6H10O5)n, and greater amount of proteins in algae versus vascular plants causes this significant difference in the C/N ratio.[1][5][6]

Instruments

Example of devices that can be used to measure this ratio are the CHN analyzer and the continuous-flow isotope ratio mass spectrometer (CF-IRMS).[7] However, for more practical applications, desired C/N ratios can be achieved by blending common used substrates of known C/N content, which are readily available and easy to use.

By sediment type

Marine

Organic matter that is deposited in marine sediments contains a key indicator as to its source and the processes it underwent before reaching the floor as well as after deposition, its carbon to nitrogen ratio.[8][9][10][4] In the global oceans, freshly produced algae in the surface ocean typically have a carbon to nitrogen ratio of about 4 to 10.[9] However, it has been observed that only 10% of this organic matter (algae) produced in the surface ocean sinks to the deep ocean without being degraded by bacteria in transit, and only about 1% is permanently buried in the sediment. An important process called sediment diagenesis accounts for the other 9% of organic carbon that sank to the deep ocean floor, but was not permanently buried, that is 9% of the total organic carbon produced is degraded in the deep ocean.[11] The microbial communities utilizing the sinking organic carbon as an energy source, are partial to nitrogen-rich compounds because much of these bacterium are nitrogen-limited and much prefer it over carbon. As a result, the carbon to nitrogen ratio of sinking organic carbon in the deep ocean is elevated compared to fresh surface ocean organic matter that had not been degraded. An exponential increase in C/N ratios is observed with increasing water depth—with C/N ratios reaching 10 at intermediate water depths of about 1000 meters, and up to 15 in the deep ocean (deeper than about 2500 meters) [citation needed]. This elevated C/N signature is preserved in the sediment, until another form of diagenesis, post-depositional diagenesis, alters its C/N signature once again.[6] Post-depositional diagenesis occurs in organic-carbon-poor marine sediments where bacteria are able to oxidize organic matter in aerobic conditions as an energy source. The oxidation reaction proceeds as follows: CH2O + H2O → CO2 + 4H+ + 4e−, with a standard free energy of –27.4 kJ mol−1 (half reaction).[11] Once all of the oxygen is used up, bacteria are able to carry out an anoxic sequence of chemical reactions as an energy source, all with negative ∆G°r values, with the reaction becoming less favorable as the chain of reactions proceeds.[11]

The same principle described above explaining the preferential degradation of nitrogen-rich organic matter occurs within the sediments, as they are more labile and are in higher demand. This principle has been utilized in paleoceanographic studies in order to identify core sites that have not experienced much microbial activity, or contamination by terrestrial sources with much higher C/N ratios.[12]

Lastly, ammonia, the product of the second reduction reaction, which reduces nitrate and produces nitrogen gas and ammonia, is easily adsorbed on clay mineral surfaces and protected from bacteria. This has been proposed as an explanation for lower than expected C/N signatures of organic carbon in sediments that have undergone post-depositional diagenesis.[6]

Ammonium produced from the remineralisation of organic material, exists in elevated concentrations (1 - >14μM) within cohesive shelf sea sediments found in the Celtic Sea (depth: 1–30 cm). The depth of sediment exceeds 1m and would be a suitable study site to carry out paleolimnology experiments with C:N.

Lacustrine

Unlike in marine sediments, diagenesis does not pose a large threat to the integrity of the C/N ratio in lacustrine sediments.[1][13] Though wood from living trees around lakes have consistently higher C/N ratios than wood buried in sediment, the change in elemental composition is not large enough to remove the vascular versus non-vascular plant signals due to the refractory nature of terrestrial organic matter.[1][14][13] Abrupt shifts in the C/N ratio down-core can be interpreted as shifts in the organic source material.

For example, two separate studies on Mangrove Lake, Bermuda and Lake Yunoko, Japan show irregular, abrupt fluctuations between C/N around 11 to around 18. These fluctuations are attributed to shifts from mainly algal dominance to land-based vascular dominance.[13][15] Results of studies that show abrupt shifts in algal dominance and vascular dominance often lead to conclusions about the state of the lake during these distinct periods of isotopic signatures. Times in which lakes are dominated by algal signals suggest the lake is a deep-water lake, while times in which lakes are dominated by vascular plant signals suggest the lake is shallow, dry, or marshy.[13] Using the C/N ratio in conjunction with other sediment observations, such as physical variations, D/H isotopic analyses of fatty acids and alkanes, and δ13C analyses on similar biomarkers can lead to further regional climate interpretations that describe the larger phenomena at play.

Soil

In microbial communities like soil, the C:N ratio is a key indicator as it describes a balance between energetic foods (represented by carbon) and material to build protein with (represented by nitrogen). An optimal C:N ratio of around 24:1 provides for higher microbial activity.[16][17]

The C:N ratio of soil can be modified by the addition of materials such as compost, manure, and mulch. A feedstock with a near-optimal C:N ratio will be consumed quickly. Any excess C will cause the N originally in the soil to be consumed, competing with the plant for nutrients (immobilization) – at least temporarily until the microbes die. Any excess N, on the other hand, will usually just be left behind (mineralization), but too much excess may result in losses to leaching. The recommended C:N ratio for soil materials is therefore 30:1. A soil test may be done to find the C:N ratio of soil itself.[16]

The C:N ratio of microbes themselves is generally around 10:1.[16] A lower ratio is correlated with higher soil productivity.[18]

Compost

The role of C:N ratio in compost feedstock is similar to that of soil feedstock. The recommendation is around 20-30:1. The microbes prefer a ratio of 30-35:1,[4] but the carbon is usually not completely digested (especially in the case of lignin feedstock), hence the lowered ratio.[19]

An imbalance of C:N ratio causes a slowdown in the composting process and a drop in temperature. When the C:N ratio is less than 15:1, outgassing of ammonium may occur, creating odor and losing nitrogen.[20] A finished compost has a C:N ratio of around 10:1.[19]

Estimating C and N contents of feedstocks

The C and N contents of feedstocks is generally known from lookup tables listing common types of feedstock. It is important to deduct the moisture content if the listed value is for dry material.[19]

For foodstuffs with a nutrition analysis, the N content may be estimated from the protein content as prot% × 0.16, reversing the crude protein calculation.[21] The C content may be estimated from crude ash content (often reported in animal feed)[19] or from reported macronutrient levels as carbs% × 0.44 + fat% × 0.86 + prot% × 0.53.[22]

Given the C:N ratio and one of C and N contents, the other content may be calculated using the very definition of the ratio.[19] When only the ratio is known, one must estimate the total C+N% or one of the contents to get both values.

Managing mixed feedstocks

The C:N ratio of mixed feedstocks is calculated by summing their C and N amounts together and dividing the two results. For compost, moisture is also an important factor.[19]

References

  1. ↑ 1.0 1.1 1.2 1.3 1.4 1.5 Ishiwatari, R.; M. Uzaki (1987). "Diagenetic Changes of Lignin Compounds in a More Than 0.6 Million-Year-Old Lacustrine Sediment (Lake Biwa, Japan)". Geochimica et Cosmochimica Acta 51 (2): 321–28. doi:10.1016/0016-7037(87)90244-4. Bibcode: 1987GeCoA..51..321I. 
  2. ↑ Gray KR, Biddlestone AJ. 1973. Composting - process parameters. The Chemical Engineer. Feb. pp 71-76
  3. ↑ Stewart, Keith (2006). It's A Long Road to A Tomato. New York: Marlowe & Company. p. 155. ISBN:978-1-56924-330-5.
  4. ↑ 4.0 4.1 4.2 Prahl, F. G., J. R. Ertel, M. A. Goni, M. A. Sparrow, and B. Eversmeyer (1994). "Terrestrial Organic-Carbon Contributions to Sediments on the Washington Margin". Geochimica et Cosmochimica Acta 58 (14): 3035–48. doi:10.1016/0016-7037(94)90177-5. Bibcode: 1994GeCoA..58.3035P. 
  5. ↑ Zahn, R., ed (February 1999) (in en). Proceedings of the Ocean Drilling Program, 161 Scientific Results. Proceedings of the Ocean Drilling Program. 161. Ocean Drilling Program. doi:10.2973/odp.proc.sr.161.235.1999. 
  6. ↑ 6.0 6.1 6.2 Müller, P.J (June 1977). "CN ratios in Pacific deep-sea sediments: Effect of inorganic ammonium and organic nitrogen compounds sorbed by clays" (in en). Geochimica et Cosmochimica Acta 41 (6): 765–776. doi:10.1016/0016-7037(77)90047-3. Bibcode: 1977GeCoA..41..765M. 
  7. ↑ Brenna, J. T.; Corso, T. N.; Tobias, H. J.; Caimi, R. J. (September 1997). "High-precision continuous-flow isotope ratio mass spectrometry". Mass Spectrometry Reviews 16 (5): 227–258. doi:10.1002/(SICI)1098-2787(1997)16:5<227::AID-MAS1>3.0.CO;2-J. PMID 9538528. Bibcode: 1997MSRv...16..227B. 
  8. ↑ Jasper, John P.; Gagosian, Robert B. (April 1990). "The sources and deposition of organic matter in the Late Quaternary Pigmy Basin, Gulf of Mexico" (in en). Geochimica et Cosmochimica Acta 54 (4): 1117–1132. doi:10.1016/0016-7037(90)90443-O. Bibcode: 1990GeCoA..54.1117J. 
  9. ↑ 9.0 9.1 Meyers, Philip A. (June 1994). "Preservation of elemental and isotopic source identification of sedimentary organic matter" (in en). Chemical Geology 114 (3–4): 289–302. doi:10.1016/0009-2541(94)90059-0. Bibcode: 1994ChGeo.114..289M. 
  10. ↑ Dahlem. "Flux to the Seafloor", Group Report, eds. K.W. Bruland et al., pp. 210–213, 1988.
  11. ↑ 11.0 11.1 11.2 Emerson, S.; Hedges, J. (2003), "Sediment Diagenesis and Benthic Flux" (in en), Treatise on Geochemistry (Elsevier) 6: 293–319, doi:10.1016/b0-08-043751-6/06112-0, ISBN 978-0-08-043751-4, Bibcode: 2003TrGeo...6..293E 
  12. ↑ Raymo, M.E.; Grant, B.; Horowitz, M.; Rau, G.H. (April 1996). "Mid-Pliocene warmth: stronger greenhouse and stronger conveyor" (in en). Marine Micropaleontology 27 (1–4): 313–326. doi:10.1016/0377-8398(95)00048-8. Bibcode: 1996MarMP..27..313R. 
  13. ↑ 13.0 13.1 13.2 13.3 Meyers, Philip A., and Ryoshi Ishiwatari (1993). "Lacustrine organic geochemistry—an overview of indicators of organic matter sources and diagenesis in lake sediments". Organic Geochemistry 20 (7): 867–900. doi:10.1016/0146-6380(93)90100-P. https://deepblue.lib.umich.edu/bitstream/2027.42/30617/1/0000257.pdf. 
  14. ↑ Meyers, Philip A. (June 1994). "Preservation of elemental and isotopic source identification of sedimentary organic matter" (in en). Chemical Geology 114 (3–4): 289–302. doi:10.1016/0009-2541(94)90059-0. Bibcode: 1994ChGeo.114..289M. 
  15. ↑ Ishiwatari, Ryoshi; Takamatsu, Nobuki; Ishibashi, Tomoko (1977). "Separation of Autochthonous and Allochthonous Materials in Lacustrine Sediments by Density Differences" (in ja). Japanese Journal of Limnology 38 (3): 94–99. doi:10.3739/rikusui.38.94. ISSN 0021-5104. http://www.jstage.jst.go.jp/article/rikusui1931/38/3/38_3_94/_article/-char/ja/. 
  16. ↑ 16.0 16.1 16.2 "Carbon to Nitrogen Ratios in Cropping Systems". https://www.nrcs.usda.gov/Internet/FSE_DOCUMENTS/nrcseprd331820.pdf. 
  17. ↑ "Carbon to Nitrogen Ratio (C:N)". https://soilhealthnexus.org/resources/soil-properties/soil-chemical-properties/carbon-to-nitrogen-ratio-cn/. 
  18. ↑ Li, Yong; Wu, Jinshui; Shen, Jianlin; Liu, Shoulong; Wang, Cong; Chen, Dan; Huang, Tieping; Zhang, Jiabao (December 2016). "Soil microbial C:N ratio is a robust indicator of soil productivity for paddy fields". Scientific Reports 6 (1): 35266. doi:10.1038/srep35266. PMID 27739462. Bibcode: 2016NatSR...635266L. 
  19. ↑ 19.0 19.1 19.2 19.3 19.4 19.5 "C/N Ratio". http://compost.css.cornell.edu/calc/cn_ratio.html. 
  20. ↑ Haug, Roger (1993). The Practical Handbook of Compost Engineering. CRC Press. ISBN 9780873713733. https://books.google.com/books?id=MX_jbemODmAC&q=ammonium+phosphate+compost&pg=PA249. Retrieved 16 October 2020. 
  21. ↑ D. Julian McClements. "Analysis of Proteins". University of Massachusetts Amherst. http://www-unix.oit.umass.edu/~mcclemen/581Proteins.html. 
  22. ↑ Rouwenhorst, R. J.; Jzn, J. F.; Scheffers, W. A.; van Dijken, J. P. (Feb–Mar 1991). "Determination of protein concentration by total organic carbon analysis". Journal of Biochemical and Biophysical Methods 22 (2): 119–128. doi:10.1016/0165-022x(91)90024-q. PMID 2061559. 

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