Highly branched isoprenoids (HBIs) are long-chain alkenes produced by a small number of marine diatoms. [1] [2] [3] 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. [4]
Highly branched isoprenoids are a type of lipid produced by marine diatoms. Highly branched isoprenoids are biomarkers, and their presence or absence in sedimentary and ice records can be used as a direct proxy for the presence of sea ice. Generally, the highly branched isoprenoids that are used as sea ice proxies are 25-carbon molecules containing one to three double bonds. The longest carbon chains in the C25 highly branched isoprenoids used for sea ice reconstructions are 15 carbons, but these molecules are highly branched and have shorter carbon chains attached to the primary carbon chain. There are 3 C25 highly branched isoprenoids used as ice proxies: a C25 monoene (HBI I), a C25 diene (HBI II), and a C25 triene (HBI III). Highly branched isoprenoid I and II are unique in that they are primarily produced by sympagic diatoms. Sympagic diatoms live in channels at the base of sea ice, making them a highly accurate proxy for sea ice. During the spring, highly branched isoprenoids are produced by diatoms in the sea ice. [5] In the summer, the ice melts, releasing the highly branched isoprenoids into the water column, where they sink and are then deposited in the sediments. [5] Highly branched isoprenoids I and II are generally absent from regions which experience no sea ice cover, supporting their use as a proxy for seasonal sea ice. Highly branched isoprenoid III is produced by pelagic algae, or algae that thrives in the open ocean. [6] Highly branched isoprenoid III can be used as a biomarker for seasonal sea ice in the open ocean. [5]
Highly branched isoprenoids were first discovered in 1976 by Patrick Gearing in sediments in the Gulf of Mexico off the coast of Florida in a survey of hydrocarbons in shelf sediments. [7] Following this initial identification, highly branched isoprenoids were identified in a variety of marine environments, such as in the Puget Sound, Antarctica, Spain, and Peru. [1] C25 Highly branched isoprenoids were first identified in marine diatoms by John Volkman in 1994, when he isolated seven different C25 highly branched isoprenoids from the marine diatom Haslea ostrearia. [1] This provided initial evidence that highly branched isoprenoids are produced by marine diatoms.
Currently, the precise biological functions of highly branched isoprenoids are not well-understood. Highly branched isoprenoids are a type of isoprenoid lipid, which have a variety of vital biological functions. Isoprenoids are important in regulating gene expression, making up cell membranes, and are important in electron transport and photosynthesis. [8]
Names | |
---|---|
IUPAC name 2,6,10,14-tetramethyl-7-(3-methylpent-4-enyl)pentadecane | |
Identifiers | |
3D model (JSmol) | |
ChemSpider | |
PubChem CID | |
| |
| |
Properties | |
C25H50 | |
Molar mass | 350.675 g·mol−1 |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). |
Highly branched isoprenoid (HBI I), a C25 monoene, is also known as IP25 (ice proxy with 25 carbon atoms). IP25 serves as a biomarker for ice conditions in the Arctic. [4] This highly branched isoprenoid is characterized by a single double bond and was first identified in marine diatoms by Thomas Brown in 2014. [3] A variety of diatoms have been shown to produce IP25, with the majority of highly branched isoprenoids produced by the Arctic diatoms Haslea crucigeroides, Haslea spicula, Haslea kjellmanii, and Pleurosigma stuxbergii var. rhomboids. [3] Despite the fact that these species do not comprise much of the sympagic diatom communities globally, they are common in the Arctic. [3] To date, IP25 has been identified in over 500 Arctic samples. [5]
Names | |
---|---|
IUPAC name 2,10,14-trimethyl-6-methylidene-7-(3-methylpent-4-enyl)pentadecane | |
Identifiers | |
3D model (JSmol) | |
ChemSpider | |
PubChem CID | |
| |
| |
Properties | |
C25H48 | |
Molar mass | 348.659 g·mol−1 |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). |
Highly branched isoprenoid II (HBI II), a C25 diene, is also known as IPSO25 (ice proxy for the Southern Ocean with 25 carbon atoms). IPSO25 is a biomarker proxy for paleo ice in the Southern Ocean. IPSO25 has also been found to co-occur with IP25 in the Arctic. [3] HBI II contains two double bonds and was first identified in marine diatoms by Simon Belt in 2016. [9] The primary source of IPSO25 the sympagic diatom Berkeleya adeliensis, which lives within platelet ice. [9] The IPSO25 proxy is a less-developed biomarker than IP25, and its Arctic sources are unclear. IPSO25 has also been identified in the diatom Haslea ostrearia and in sediments in non-polar locations, indicating that more work is needed to fully understand and develop IPSO25 as a paleo ice proxy. [10] [11]
Names | |
---|---|
IUPAC name (Z,9E)-2,6,10,14-tetramethyl-9-(3-methylpent-4-enylidene)pentadec-6-ene | |
Identifiers | |
3D model (JSmol) | |
ChemSpider | |
PubChem CID | |
| |
| |
Properties | |
C25H46 | |
Molar mass | 346.643 g·mol−1 |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). |
Highly branched isoprenoid III (HBI III), a C25 triene, is a biomarker useful for the analysis of the marginal ice zone (MIZ), a zone between the open ocean and sea ice. Highly branched isoprenoid III is primarily produced by pelagic algae of the genus Rhizosolenia, particularly Rhizsolenia setigera, Rhizosolenia herbetata f. semispina, and Rhizosolenia polydactyla. [6] Its source was determined by Simon Belt in 2017, who isolated highly branched isoprenoid III from phytoplankton samples from western Svalbard and the South Atlantic. [6] The production of highly branched isoprenoid III appears to be enhanced in the MIZ, however why this occurs is currently not well-understood. [5] The absence of highly branched isoprenoid III in sediments is typically attributed to sea ice cover in the region, given that ice cover would not allow for pelagic algae production. [5]
Many biomarkers possess functional groups or are unsaturated, causing them to undergo diagenesis when emplaced in sediments. Highly branched isoprenoids are observed to be well-preserved in the sedimentary record. [5] Highly branched isoprenoids primarily form in the seasonal sea ice during the spring sympagic diatom blooms. When these ice sheets subsequently melt, the highly branched isoprenoids formed in the sea ice are released into the sea water. They then fall through the water column and are emplaced into the sediments, where they can be preserved. The sediment conditions impacts how well the highly branched isoprenoids are preserved. Generally, the stability of highly branched isoprenoids is dependent on their degree of unsaturation. [12] C25 trienes are more likely to undergo degradation compared to C25 monenes and dienes, and degradation is enhanced by increasing temperature and exposure to light, which results in oxidation. [12] The mono-unsaturated C25 IP25 is the least reactive highly branched isoprenoid, and thus is the most resistant to degradation and is best preserved in sediments. [12]
Highly branched isoprenoids, particularly highly branched isoprenoid I, are hypothesized to have long-term stability. While most studies to date have focused on studying highly branched isoprenoids in sediments from the Holocene, highly branched isoprenoids have been detected, measured, and analyzed in 12 million year old sediments from the late Miocene. [13] More work is necessary to determine whether highly branched isoprenoids can be preserved beyond 12 million years, but it is likely that their time to degradation is dependent on the local sediment conditions.
Highly branched isoprenoids and other organic materials can be extracted from sediments for analysis. Coupled gas chromatography and mass spectrometry can be utilized to analyze the organic materials present in the sediments. Peaks can be identified using a gas chromatograph and a mass spectrum, which provide information about the retention time and mass-to-charge ratio of the organic compounds present in the molecule. This allows for the identification of highly branched isoprenoids within a material. To identify highly branched isoprenoids in sediments, typically selective ion monitoring (SIM) is utilized. [3] SIM gathers data at masses of interest within an expected retention time window, enabling the identification and quantification of compounds with high sensitivity. Highly branched isoprenoid I, highly branched isoprenoid II, and highly branched isoprenoid III are identified and quantified via SIM using the characteristic mass spectrum peaks at m/z = 350, 348, and 346, respectively. [5]
Carbon isotopic measurements can be utilized to confirm the sea ice origin of highly branched isoprenoids. These carbon isotope measurements are obtained using an Isotope Ratio Mass Spectrometer. Highly branched isoprenoids with a sea ice origin are enriched in [[δ13C]] in both sea ice and in sediments. [5] The measurement of δ13C values enables a diagnostic determination of whether the highly branched isoprenoid came from sea ice.
Highly branched isoprenoid I has been observed to be enriched in 13C. δ13C values range from −16.9 to −22.7‰ in sea ice and −16.3 to −23.2‰ in sediments. [15] [16] This enrichment has been hypothesized to be in part a result of the fact that the marine diatoms that produce highly branched isoprenoid I live under CO2-limited conditions. [15] Temperature and diatom growth rate may also play a role in observed isotopic composition of highly branched isoprenoid I, but more work is needed to fully understand the drivers of the observed δ13C values. [15]
Highly branched isoprenoid II has a characteristic carbon isotope composition, with measured δ13C values ranging from −5.7 to −8.5‰. [17] This value is indicative of an enrichment in 13C. This enrichment has also been observed for highly branched isoprenoid II in sediments and in waters near melting sea ice. [17] [18] This enrichment likely results from the CO2-limited conditions under which the diatom producers of highly branched isoprenoid II grow. [17] This distinctive isotopic composition provides strong evidence for the sea ice origin of highly branched isoprenoid II, making it a good proxy for sea ice around Antarctica.
Highly branched isoprenoid III is depleted in δ13C, with values ranging from −35 to −40‰. [17] Highly branched isoprenoid III is depleted in δ13C because it is not produced under CO2-limited conditions, so the depletion is a result of biological fractionation. [17]
Currently, more than 60 paleo sea ice records that have been constructed based on IP25 over the Holocene, the Mid-Pleistocene Transition, the Pliocene/Pleistocene boundary, and the late Miocene. [19] The presence of IP25 in sediments is a direct proxy for the presence of seasonal sea ice cover. One study utilized the concentration of IP25 in sediments to reconstruct sea-ice records in the western North Pacific and Bering Sea over the past 18,000 years. [20] Researchers from Germany obtained sediment samples from the North Pacific Ocean and Bering Sea during a Sonne cruise in 2009. [20] IP25 was identified in the samples using GC/MS, and the sediments were dated using a chronostratigraphic approach, X-ray fluorescence, and radiocarbon dating of planktonic foraminifera. [20] The researchers found that variations in the concentration of the sea-ice proxy IP25 were consistent with known temperature variations based on other evidence, such as δ18O values and biogenic opal data. [20] Generally, during cold intervals, the concentration of IP25 in sediments was elevated, indicating more extensive sea ice cover. [20] More specifically, between 18,000 and 15,000 years ago, IP25 concentrations were relatively high, but decreased between 14,700 and 12,900 years ago during the Bølling/Allerød warming period. [20] At 12,500 years ago, a significant increase in IP25 concentration was detected in the sediments, consistent with the start of the Younger Dryas period, which marked a return to glacial conditions. [20] IP25 concentrations decreased to approximately 0 11,500 years ago, marking the end of the Younger Dryas. For the entire Holocene, IP25 concentrations have remained low, which is accordant with the lack of extensive ice cover throughout this period. [20] This reconstruction is consistent with other paleoclimate proxies and known climate variations, demonstrating the ability of the IP25 proxy to reconstruct paleo ice records.
Benthos, also known as benthon, is the community of organisms that live on, in, or near the bottom of a sea, river, lake, or stream, also known as the benthic zone. This community lives in or near marine or freshwater sedimentary environments, from tidal pools along the foreshore, out to the continental shelf, and then down to the abyssal depths.
The Paleocene–Eocene thermal maximum (PETM), alternatively ”Eocene thermal maximum 1 (ETM1)“ and formerly known as the "Initial Eocene" or “Late Paleocene thermal maximum", was a geologically brief time interval characterized by a 5–8 °C global average temperature rise and massive input of carbon into the ocean and atmosphere. The event began, now formally codified, at the precise time boundary between the Paleocene and Eocene geological epochs. The exact age and duration of the PETM remain uncertain, but it occurred around 55.8 million years ago (Ma) and lasted about 200 thousand years (Ka).
Ice algae are any of the various types of algal communities found in annual and multi-year sea, and terrestrial lake ice or glacier ice.
TEX86 is an organic paleothermometer based upon the membrane lipids of mesophilic marine Nitrososphaerota (formerly "Thaumarchaeota", "Marine Group 1 Crenarchaeota").
Paleoceanography is the study of the history of the oceans in the geologic past with regard to circulation, chemistry, biology, geology and patterns of sedimentation and biological productivity. Paleoceanographic studies using environment models and different proxies enable the scientific community to assess the role of the oceanic processes in the global climate by the re-construction of past climate at various intervals. Paleoceanographic research is also intimately tied to paleoclimatology.
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.
γ-Carotene (gamma-carotene) is a carotenoid, and is a biosynthetic intermediate for cyclized carotenoid synthesis in plants. It is formed from cyclization of lycopene by lycopene cyclase epsilon. Along with several other carotenoids, γ-carotene is a vitamer of vitamin A in herbivores and omnivores. Carotenoids with a cyclized, beta-ionone ring can be converted to vitamin A, also known as retinol, by the enzyme beta-carotene 15,15'-dioxygenase; however, the bioconversion of γ-carotene to retinol has not been well-characterized. γ-Carotene has tentatively been identified as a biomarker for green and purple sulfur bacteria in a sample from the 1.640 ± 0.003-Gyr-old Barney Creek Formation in Northern Australia which comprises marine sediments. Tentative discovery of γ-carotene in marine sediments implies a past euxinic environment, where water columns were anoxic and sulfidic. This is significant for reconstructing past oceanic conditions, but so far γ-carotene has only been potentially identified in the one measured sample.
Archaeol is a diether composed of two phytanyl chains linked to the sn-2 and sn-3 positions of glycerol. As its phosphate ester, it is a common component of the membranes of archaea.
Desmosterol (Cholesta-5,24-dien-3β-ol) is a lipid present in the membrane of phytoplankton and an intermediate product in cholesterol synthesis in mammal cells. Structurally, desmosterol has a similar backbone to cholesterol, with the exception of an additional double bond in the structure of desmosterol.
Dinosterol (4α,23,24-trimethyl-5α-cholest-22E-en-3β-ol) is a 4α-methyl sterol that is produced by several genera of dinoflagellates and is rarely found in other classes of protists. The steroidal alkane, dinosterane, is the 'molecular fossil' of dinosterol, meaning that dinosterane has the same carbon skeleton as dinosterol, but lacks dinosterol's hydroxyl group and olefin functionality. As such, dinosterane is often used as a biomarker to identify the presence of dinoflagelletes in sediments.
Crocetane, or 2,6,11,15-tetramethylhexadecane, is an isoprenoid hydrocarbon compound. Unlike its isomer phytane, crocetane has a tail-to-tail linked isoprenoid skeleton. Crocetane has been detected in modern sediments and geological records as a biomarker, often associated with anaerobic methane oxidation.
Okenane, the diagenetic end product of okenone, is a biomarker for Chromatiaceae, the purple sulfur bacteria. These anoxygenic phototrophs use light for energy and sulfide as their electron donor and sulfur source. Discovery of okenane in marine sediments implies a past euxinic environment, where water columns were anoxic and sulfidic. This is potentially tremendously important for reconstructing past oceanic conditions, but so far okenane has only been identified in one Paleoproterozoic rock sample from Northern Australia.
24-Norcholestane, a steroid derivative, is used as a biomarker to constrain the source age of sediments and petroleum through the ratio between 24-norcholestane and 27-norcholestane, especially when used with other age diagnostic biomarkers, like oleanane. While the origins of this compound are still unknown, it is thought that they are derived from diatoms due to their identification in diatom rich sediments and environments. In addition, it was found that 24-norcholestane levels increased in correlation with diatom evolution. Another possible source of 24-norcholestane is from dinoflagellates, albeit to a much lower extent.
Crenarchaeol is a glycerol biphytanes glycerol tetraether (GDGT) biological membrane lipid. Together with archaeol, crenarcheol comprises a major component of archaeal membranes. Archaeal membranes are distinct from those of bacteria and eukaryotes because they contain isoprenoid GDGTs instead of diacyl lipids, which are found in the other domains. It has been proposed that GDGT membrane lipids are an adaptation to the high temperatures present in the environments that are home to extremophile archaea
Lycopane (C40H82; 2,6,10,14,19,23,27,31-octamethyldotriacontane), a 40 carbon alkane isoprenoid, is a widely present biomarker that is often found in anoxic settings. It has been identified in anoxically deposited lacustrine sediments (such as the Messel formation and the Condor oil shale deposit). It has been found in sulfidic and anoxic hypersaline environments (such as the Sdom Formation). It has been widely identified in modern marine sediments, including the Peru upwelling zone, the Black Sea, and the Cariaco Trench. It has been found only rarely in crude oils.
Chamaecydin is a chemical compound with the molecular formula C30H40O3. It is made up of three six-membered rings and two five-membered rings and has one polar hydroxyl functional group. It is well preserved in the rock record and is only found in a specific family of conifers, the swamp cypress subfamily. The presence and abundance of chamaecydin in the rock record can reveal environmental changes in ancient biomes.
Hydroxyarchaeol is a core lipid unique to archaea, similar to archaeol, with a hydroxide functional group at the carbon-3 position of one of its ether side chains. It is found exclusively in certain taxa of methanogenic archaea, and is a common biomarker for methanogenesis and methane-oxidation. Isotopic analysis of hydroxyarchaeol can be informative about the environment and substrates for methanogenesis.
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.
Global paleoclimate indicators are the proxies sensitive to global paleoclimatic environment changes. They are mostly derived from marine sediments. Paleoclimate indicators derived from terrestrial sediments, on the other hand, are commonly influenced by local tectonic movements and paleogeographic variations. Factors governing the Earth's climate system include plate tectonics, which controls the configuration of continents, the interplay between the atmosphere and the ocean, and the Earth's orbital characteristics. Global paleoclimate indicators are established based on the information extracted from the analyses of geologic materials, including biological, geochemical and mineralogical data preserved in marine sediments. Indicators are generally grouped into three categories; paleontological, geochemical and lithological.
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.