A biogenic substance is a product made by or of life forms. While the term originally was specific to metabolite compounds that had toxic effects on other organisms, [1] it has developed to encompass any constituents, secretions, and metabolites of plants or animals. [2] In context of molecular biology, biogenic substances are referred to as biomolecules. They are generally isolated and measured through the use of chromatography and mass spectrometry techniques. [3] [4] Additionally, the transformation and exchange of biogenic substances can by modelled in the environment, particularly their transport in waterways. [5]
The observation and measurement of biogenic substances is notably important in the fields of geology and biochemistry. A large proportion of isoprenoids and fatty acids in geological sediments are derived from plants and chlorophyll, and can be found in samples extending back to the Precambrian. [4] These biogenic substances are capable of withstanding the diagenesis process in sediment, but may also be transformed into other materials. [4] This makes them useful as biomarkers for geologists to verify the age, origin and degradation processes of different rocks. [4]
Biogenic substances have been studied as part of marine biochemistry since the 1960s, [6] which has involved investigating their production, transport, and transformation in the water, [5] and how they may be used in industrial applications. [6] A large fraction of biogenic compounds in the marine environment are produced by micro and macro algae, including cyanobacteria. [6] Due to their antimicrobial properties they are currently the subject of research in both industrial projects, such as for anti-fouling paints, [1] or in medicine. [6]
During a meeting of the New York Academy of Sciences' Section of Geology and Mineralogy in 1903, geologist Amadeus William Grabau proposed a new rock classification system in his paper 'Discussion of and Suggestions Regarding a New Classification of Rocks'. [7] Within the primary subdivision of "Endogenetic rocks" – rocks formed through chemical processes – was a category termed "Biogenic rocks", which was used synonymously with "Organic rocks". Other secondary categories were "Igneous" and "Hydrogenic" rocks. [7]
In the 1930s German chemist Alfred E. Treibs first detected biogenic substances in petroleum as part of his studies of porphyrins. [4] Based on this research, there was a later increase in the 1970s in the investigation of biogenic substances in sedimentary rocks as part of the study of geology. [4] This was facilitated by the development of more advanced analytical methods, and led to greater collaboration between geologists and organic chemists in order to research the biogenic compounds in sediments. [4]
Researchers additionally began to investigate the production of compounds by microorganisms in the marine environment during the early 1960s. [6] By 1975, different research areas had developed in the study of marine biochemistry. These were "marine toxins, marine bioproducts and marine chemical ecology". [6] Following this in 1994, Teuscher and Lindequist defined biogenic substances as "chemical compounds which are synthesised by living organisms and which, if they exceed certain concentrations, cause temporary or permanent damage or even death of other organisms by chemical or physicochemical effects" in their book, Biogene Gifte. [1] [8] This emphasis in research and classification on the toxicity of biogenic substances was partly due to the cytotoxicity-directed screening assays that were used to detect the biologically active compounds. [6] The diversity of biogenic products has since been expanded from cytotoxic substances through the use of alternative pharmaceutical and industrial assays. [6]
Through studying the transport of biogenic substances in the Tatar Strait in the Sea of Japan, a Russian team noted that biogenic substances can enter the marine environment due to input from either external sources, transport inside the water masses, or development by metabolic processes within the water. [5] They can likewise be expended due to biotransformation processes, or biomass formation by microorganisms. In this study the biogenic substance concentrations, transformation frequency, and turnover were all highest in the upper layer of the water. Additionally, in different regions of the strait the biogenic substances with the highest annual transfer were constant. These were O2, DOC, and DISi, which are normally found in large concentrations in natural water. [5] The biogenic substances that tend to have lower input through the external boundaries of the strait and therefore least transfer were mineral and detrital components of N and P. These same substances take active part in biotransformation processes in the marine environment and have lower annual output as well. [5]
Organic geochemists also have an interest in studying the diagenesis of biogenic substances in petroleum and how they are transformed in sediment and fossils. [4] While 90% of this organic material is insoluble in common organic solvents – called kerogen – 10% is in a form that is soluble and can be extracted, from where biogenic compounds can then be isolated. [4] Saturated linear fatty acids and pigments have the most stable chemical structures and are therefore suited to withstanding degradation from the diagenesis process and being detected in their original forms. [4] However, macromolecules have also been found in protected geological regions. [4] Typical sedimentation conditions involve enzymatic, microbial and physicochemical processes as well as increased temperature and pressure, which lead to transformations of biogenic substances. [4] For example, pigments that arise from dehydrogenation of chlorophyll or hemin can be found in many sediments as nickel or vanadyl complexes. [4] A large proportion of the isoprenoids in sediments are also derived from chlorophyll. Similarly, linear saturated fatty acids discovered in the Messel oil shale of the Messel Pit in Germany arise from organic material of vascular plants. [4]
Additionally, alkanes and isoprenoids are found in soluble extracts of Precambrian rock, indicating the probable existence of biological material more than three billion years ago. [4] However, there is the potential that these organic compounds are abiogenic in nature, especially in Precambrian sediments. While Studier et al.'s (1968) simulations of the synthesis of isoprenoids in abiogenic conditions did not produce the long-chain isoprenoids used as biomarkers in fossils and sediments, traces of C9-C14 isoprenoids were detected. [11] It is also possible for polyisoprenoid chains to be stereoselectively synthesised using catalysts such as Al(C2H5)3 – VCl3. [12] However, the probability of these compounds being available in the natural environment is unlikely. [4]
The different biomolecules that make up a plant's biogenic substances – particularly those in seed exudates - can be identified by using different varieties of chromatography in a lab environment. [3] For metabolite profiling, gas chromatography-mass spectrometry is used to find flavonoids such as quercetin. [3] Compounds can then be further differentiated using reversed-phase high-performance liquid chromatography-mass spectrometry. [3]
When it comes to measuring biogenic substances in a natural environment such as a body of water, a hydroecological [13] CNPSi model can be used to calculate the spatial transport of biogenic substances, in both the horizontal and vertical dimensions. [5] This model takes into account the water exchange and flow rate, and yields the values of biogenic substance rates for any area or layer of the water for any month. There are two main evaluation methods involved: measuring per unit water volume (mg/m3 year) and measuring substances per entire water volume of layer (t of element/year). [5] The former is mostly used to observe biogenic substance dynamics and individual pathways for flux and transformations, and is useful when comparing individual regions of the strait or waterway. The second method is used for monthly substance fluxes and must take into account that there are monthly variations in the water volume in the layers. [5]
In the study of geochemistry, biogenic substances can be isolated from fossils and sediments through a process of scraping and crushing the target rock sample, then washing with 40% hydrofluoric acid, water, and benzene/methanol in the ratio 3:1. [4] Following this, the rock pieces are ground and centrifuged to produce a residue. Chemical compounds are then derived through various chromatography and mass spectrometry separations. [4] However, extraction should be accompanied by rigorous precautions to ensure there is no amino acid contaminants from fingerprints, [14] or silicone contaminants from other analytical treatment methods. [4]
Metabolites produced by marine algae have been found to have many antimicrobial properties. [1] This is because they are produced by the marine organisms as chemical deterrents and as such contain bioactive compounds. The principal classes of marine algae that produce these types of secondary metabolites are Cyanophyceae, Chlorophyceae and Rhodophyceae. [1] Observed biogenic products include polyketides, amides, alkaloids, fatty acids, indoles and lipopeptides. [1] For example, over 10% of compounds isolated from Lyngbya majuscula , which is one of the most abundant cyanobacteria, have antifungal and antimicrobial properties. [1] [6] Additionally, a study by Ren et al. (2002) tested halogenated furanones produced by Delisea pulchra from the Rhodophyceae class against the growth of Bacillus subtilis . [15] [1] When applied at a 40 μg/mL concentration, the furanone inhibited the formation of a biofilm by the bacteria and reduced the biofilm's thickness by 25% and the number of live cells by 63%. [15]
These characteristics then have the potential to be utilised in man-made materials, such as making anti-fouling paints without the environment-damaging chemicals. [1] Environmentally safe alternatives are needed to TBT (tin-based antifouling agent) which releases toxic compounds into water and the environment and has been banned in several countries. [1] A class of biogenic compounds that has had a sizeable effect against the bacteria and microalgae that cause fouling are acetylene sesquiterpenoid esters produced by Caulerpa prolifera (from the Chlorophyceae class), which Smyrniotopoulos et al. (2003) observed inhibiting bacterial growth with up to 83% of the efficacy of TBT oxide. [16]
Current research also aims to produce these biogenic substances on a commercial level using metabolic engineering techniques. [1] By pairing these techniques with biochemical engineering design, algae and their biogenic substances can be produced on a large scale using photobioreactors. [1] Different system types can be used to yield different biogenic products. [1]
Photobioreactor type | Algae species cultured | Product | Reference |
---|---|---|---|
Seaweed type polyurethane | Scytonema sp.TISTR 8208 | Cyclic dodecapeptide antibiotic effective against Gram-positive bacteria, filamentous fungi and pathogenic yeasts | Chetsumon et al. (1998) [17] |
Stirred tank | Agardhiella subulata | Biomass | Huang and Rorrer (2003) [18] |
Airlift | Gyrodinium impundicum | Sulphated exopolysaccharides for antiviral action against encephalomyocarditis virus | Yim et al. (2003) [19] |
Large scale outdoor | Haematococcus pluvialis | Astaxanthin compound | Miguel (2000) [20] |
In the field of paleochemotaxonomy the presence of biogenic substances in geological sediments is useful for comparing old and modern biological samples and species. [4] These biological markers can be used to verify the biological origin of fossils and serve as paleo-ecological markers. For example, the presence of pristane indicates that the petroleum or sediment is of marine origin, while biogenic material of non-marine origin tends to be in the form of polycyclic compounds or phytane. [21] The biological markers also provide valuable information about the degradation reactions of biological material in geological environments. [4] Comparing the organic material between geologically old and recent rocks shows the conservation of different biochemical processes. [4]
Another application of biogenic substances is in the synthesis of metallic nanoparticles. [3] The current chemical and physical production methods for nanoparticles used are costly and produce toxic waste and pollutants in the environment. [22] Additionally, the nanoparticles that are produced can be unstable and unfit for use in the body. [23] Using plant-derived biogenic substances aims to create an environmentally-friendly and cost-effective production method. [3] The biogenic phytochemicals used for these reduction reactions can be derived from plants in numerous ways, including a boiled leaf broth, [24] biomass powder, [25] whole plant immersion in solution, [23] or fruit and vegetable juice extracts. [26] C. annuum juices have been shown to produce Ag nanoparticles at room temperature when treated with silver ions and additionally deliver essential vitamins and amino acids when consumed, making them a potential nanomaterials agent. [3] Another procedure is through the use of a different biogenic substance: the exudate of germinating seeds. When seeds are soaked, they passively release phytochemicals into the surrounding water, which after reaching equilibrium can be mixed with metal ions to synthesise metallic nanoparticles. [27] [3] M. sativa exudate in particular has had success in effectively producing Ag metallic particles, while L. culinaris is an effective reactant for manufacturing Au nanoparticles. [3] This process can also be further adjusted by manipulating factors such as pH, temperature, exudate dilution and plant origin to produce different shapes of nanoparticles, including triangles, spheres, rods, and spirals. [3] These biogenic metallic nanoparticles then have applications as catalysts, glass window coatings to insulate heat, in biomedicine, and in biosensor devices. [3]
Chemical class | Compound | Source | Reference |
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Lipopeptide [1] |
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Fatty acid [1] |
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Terpene [6] |
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Alkaloid [1] |
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Ketone [4] |
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An abiogenic substance or process does not result from the present or past activity of living organisms. Abiogenic products may, e.g., be minerals, other inorganic compounds, as well as simple organic compounds (e.g. extraterrestrial methane, see also abiogenesis).
Bioaccumulation is the gradual accumulation of substances, such as pesticides or other chemicals, in an organism. Bioaccumulation occurs when an organism absorbs a substance faster than it can be lost or eliminated by catabolism and excretion. Thus, the longer the biological half-life of a toxic substance, the greater the risk of chronic poisoning, even if environmental levels of the toxin are not very high. Bioaccumulation, for example in fish, can be predicted by models. Hypothesis for molecular size cutoff criteria for use as bioaccumulation potential indicators are not supported by data. Biotransformation can strongly modify bioaccumulation of chemicals in an organism.
Diagenesis is the process that describes physical and chemical changes in sediments first caused by water-rock interactions, microbial activity, and compaction after their deposition. Increased pressure and temperature only start to play a role as sediments become buried much deeper in the Earth's crust. In the early stages, the transformation of poorly consolidated sediments into sedimentary rock (lithification) is simply accompanied by a reduction in porosity and water expulsion, while their main mineralogical assemblages remain unaltered. As the rock is carried deeper by further deposition above, its organic content is progressively transformed into kerogens and bitumens.
Kerogen is solid, insoluble organic matter in sedimentary rocks. It consists of a variety of organic materials, including dead plants, algae, and other microorganisms, that have been compressed and heated by geological processes. All the kerogen on earth is estimated to contain 1016 tons of carbon. This makes it the most abundant source of organic compounds on earth, exceeding the total organic content of living matter 10,000-fold.
A biogeochemical cycle, or more generally a cycle of matter, is the movement and transformation of chemical elements and compounds between living organisms, the atmosphere, and the Earth's crust. Major biogeochemical cycles include the carbon cycle, the nitrogen cycle and the water cycle. In each cycle, the chemical element or molecule is transformed and cycled by living organisms and through various geological forms and reservoirs, including the atmosphere, the soil and the oceans. It can be thought of as the pathway by which a chemical substance cycles the biotic compartment and the abiotic compartments of Earth. The biotic compartment is the biosphere and the abiotic compartments are the atmosphere, lithosphere and hydrosphere.
The abiogenic petroleum origin hypothesis proposes that most of earth's petroleum and natural gas deposits were formed inorganically, commonly known as abiotic oil. Scientific evidence overwhelmingly supports a biogenic origin for most of the world's petroleum deposits. Mainstream theories about the formation of hydrocarbons on earth point to an origin from the decomposition of long-dead organisms, though the existence of hydrocarbons on extraterrestrial bodies like Saturn's moon Titan indicates that hydrocarbons are sometimes naturally produced by inorganic means. A historical overview of theories of the abiogenic origins of hydrocarbons has been published.
Humic substances (HS) are coloured recalcitrant organic compounds naturally formed during long-term decomposition and transformation of biomass residues. The colour of humic substances varies from yellow to brown to black. The term comes from humus, which in turn comes from the Latin word humus, meaning "soil, earth". Humic substances represent the major part of organic matter in soil, peat, coal, and sediments, and are important components of dissolved natural organic matter (NOM) in lakes, rivers, and sea water.
A microfossil is a fossil that is generally between 0.001 mm and 1 mm in size, the visual study of which requires the use of light or electron microscopy. A fossil which can be studied with the naked eye or low-powered magnification, such as a hand lens, is referred to as a macrofossil.
Phosphorite, phosphate rock or rock phosphate is a non-detrital sedimentary rock that contains high amounts of phosphate minerals. The phosphate content of phosphorite (or grade of phosphate rock) varies greatly, from 4% to 20% phosphorus pentoxide (P2O5). Marketed phosphate rock is enriched ("beneficiated") to at least 28%, often more than 30% P2O5. This occurs through washing, screening, de-liming, magnetic separation or flotation. By comparison, the average phosphorus content of sedimentary rocks is less than 0.2%.
The important sulfur cycle is a biogeochemical cycle in which the sulfur moves between rocks, waterways and living systems. It is important in geology as it affects many minerals and in life because sulfur is an essential element (CHNOPS), being a constituent of many proteins and cofactors, and sulfur compounds can be used as oxidants or reductants in microbial respiration. The global sulfur cycle involves the transformations of sulfur species through different oxidation states, which play an important role in both geological and biological processes. Steps of the sulfur cycle are:
Phytane is the isoprenoid alkane formed when phytol, a chemical substituent of chlorophyll, loses its hydroxyl group. When phytol loses one carbon atom, it yields pristane. Other sources of phytane and pristane have also been proposed than phytol.
The phosphorus cycle is the biogeochemical cycle that involves the movement of phosphorus through the lithosphere, hydrosphere, and biosphere. Unlike many other biogeochemical cycles, the atmosphere does not play a significant role in the movement of phosphorus, because phosphorus and phosphorus-based materials do not enter the gaseous phase readily, as the main source of gaseous phosphorus, phosphine, is only produced in isolated and specific conditions. Therefore, the phosphorus cycle is primarily examined studying the movement of orthophosphate (PO4)3-, the form of phosphorus that is most commonly seen in the environment, through terrestrial and aquatic ecosystems.
Marine sediment, or ocean sediment, or seafloor sediment, are deposits of insoluble particles that have accumulated on the seafloor. These particles either have their origins in soil and rocks and have been transported from the land to the sea, mainly by rivers but also by dust carried by wind and by the flow of glaciers into the sea, or they are biogenic deposits from marine organisms or from chemical precipitation in seawater, as well as from underwater volcanoes and meteorite debris.
The Barberton Greenstone Belt of eastern South Africa contains some of the most widely accepted fossil evidence for Archean life. These cell-sized prokaryote fossils are seen in the Barberton fossil record in rocks as old as 3.5 billion years. The Barberton Greenstone Belt is an excellent place to study the Archean Earth due to exposed sedimentary and metasedimentary rocks.
Marine biogeochemical cycles are biogeochemical cycles that occur within marine environments, that is, in the saltwater of seas or oceans or the brackish water of coastal estuaries. These biogeochemical cycles are the pathways chemical substances and elements move through within the marine environment. In addition, substances and elements can be imported into or exported from the marine environment. These imports and exports can occur as exchanges with the atmosphere above, the ocean floor below, or as runoff from the land.
The silica cycle is the biogeochemical cycle in which biogenic silica is transported between the Earth's systems. Silicon is considered a bioessential element and is one of the most abundant elements on Earth. The silica cycle has significant overlap with the carbon cycle and plays an important role in the sequestration of carbon through continental weathering, biogenic export and burial as oozes on geologic timescales.
The deep biosphere is the part of the biosphere that resides below the first few meters of the surface. It extends down below 10 kilometers below the continental surface and 21 kilometers below the sea surface, at temperatures that may reach beyond 120 °C (248 °F) which is comparable to the maximum temperature where a metabolically active organism has been found. It includes all three domains of life and the genetic diversity rivals that on the surface.
Highly branched isoprenoids (HBIs) are long-chain alkenes produced by a small number of marine diatoms. There are a variety of highly branched isoprenoid structures, but C25 Highly branched isoprenoids containing one to three double bonds are the most common in the sedimentary record. Highly branched isoprenoids have been used as environmental proxies for sea ice conditions in the Arctic and Antarctic throughout the Holocene, and more recently, are being used to reconstruct more ancient ice records.
Glycerol dialkyl glycerol tetraether lipids (GDGTs) are a class of membrane lipids synthesized by archaea and some bacteria, making them useful biomarkers for these organisms in the geological record. Their presence, structure, and relative abundances in natural materials can be useful as proxies for temperature, terrestrial organic matter input, and soil pH for past periods in Earth history. Some structural forms of GDGT form the basis for the TEX86 paleothermometer. Isoprenoid GDGTs, now known to be synthesized by many archaeal classes, were first discovered in extremophilic archaea cultures. Branched GDGTs, likely synthesized by acidobacteriota, were first discovered in a natural Dutch peat sample in 2000.
In geology, silicification is a petrification process in which silica-rich fluids seep into the voids of Earth materials, e.g., rocks, wood, bones, shells, and replace the original materials with silica (SiO2). Silica is a naturally existing and abundant compound found in organic and inorganic materials, including Earth's crust and mantle. There are a variety of silicification mechanisms. In silicification of wood, silica permeates into and occupies cracks and voids in wood such as vessels and cell walls. The original organic matter is retained throughout the process and will gradually decay through time. In the silicification of carbonates, silica replaces carbonates by the same volume. Replacement is accomplished through the dissolution of original rock minerals and the precipitation of silica. This leads to a removal of original materials out of the system. Depending on the structures and composition of the original rock, silica might replace only specific mineral components of the rock. Silicic acid (H4SiO4) in the silica-enriched fluids forms lenticular, nodular, fibrous, or aggregated quartz, opal, or chalcedony that grows within the rock. Silicification happens when rocks or organic materials are in contact with silica-rich surface water, buried under sediments and susceptible to groundwater flow, or buried under volcanic ashes. Silicification is often associated with hydrothermal processes. Temperature for silicification ranges in various conditions: in burial or surface water conditions, temperature for silicification can be around 25°−50°; whereas temperatures for siliceous fluid inclusions can be up to 150°−190°. Silicification could occur during a syn-depositional or a post-depositional stage, commonly along layers marking changes in sedimentation such as unconformities or bedding planes.
Biphytane (or bisphytane) is a C40 isoprenoid produced from glycerol dialkyl glycerol tetraether (GDGT) degradation. As a common lipid membrane component, biphytane is widely used as a biomarker for archaea. In particular, given its association with sites of active anaerobic oxidation of methane (AOM), it is considered a biomarker of methanotrophic archaea. It has been found in both marine and terrestrial environments.
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