Analysis of carotenoid and porphyrin pigments of geochemical interest by high-performance liquid chromatography

Hajibrahim, Saleh K.; Tibbetts, P. J. C.; Watts, C.D.; Maxwell, James R.; Eglinton, G.; Colin, Henri; Guiochon, Georges

doi:10.1021/ac50026a004

Cited by 83 publications

(20 citation statements)

References 8 publications

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“…That is, methanol is known to deactivate chromatographic silica (see Purcell, 1958). Through comparing chromatographic mobility of the carotene-diols isolated from Leg 64 samples to those reported from other studies (e.g., see Fiksdahl et al, 1978;Hajibrahim et al, 1978) and to the known position of authentic chlorophyll-a on the system used herein with that reported by others (Fiksdahl et al, 1978), these compounds appear to be zeaxanthin-like (XXXII: jO,ß-carotene-3,3'-diol) and diatoxanthin-like (XXXIII: 7,8-didehydro-ß,/3-carotene-3,3'-diol) compounds. However, further study and mass spectrometric analyses are required before assigning definite structure.…”

Section: Apo-carotenoids Refers To Tentatively Identified Apo-carotenmentioning

confidence: 98%

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Geochemistry of Tetrapyrrole, Tetraterpenoid, and Perylene Pigments in Sediments from the Gulf of California: Deep Sea Drilling Project Leg 64, Sites 474, 477, 479, and 481, and Scripps Institution of Oceanography Guaymas Basin Survey Cruise Leg 3, Sites 10G and 18G

Baker¹,

Louda²

1982

Initial Reports of the Deep Sea Drilling Project, 64

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Results and discussion cover pigment analyses of 36 sediment samples recovered by Deep Sea Drilling Project Leg 64, and six samples from the Leg 64 site-survey cruise in the Guaymas Basin (Scripps Institution of Oceanography, Leg 3). Pigments investigated were tetrapyrroles, tetraterpenoids, and the PAH compound perylene.Traces of mixed nickel and copper ETIO-porphyrins were ubiquitous in all sediment samples, except for the very surface (i.e., <2 m sub-bottom), and their presence is taken as an indication of minor influxes of previously oxidized allochthonous (terrestrial) organic matter.Phorbides and chlorins isolated from Site 479 sediment samples (i.e., the oxygen-minimum locale, northeast of the Guaymas Basin) well represent the reductive diagenesis ("Treibs Scheme"; see Treibs, 1936) of chlorophyll derivatives. Three forms of pheophytin-a, plus a variety of phorbides, were found to give rise to freebase porphyrins, nickel phylloerythrin, and nickel porphyrins, with increasing depth of burial (increasing temperature).Sediments from Sites 481, 10G, and 18G yielded chlorophyll derivatives characteristic of early oxidative alterations. Included among these pigments are allomerized pheophytin-a, purpurin-18, and chlorin-p 6 .The high thermal gradient imposed upon the late Quaternary sediments of Site 477 greatly accelerated chlorophyll diagenesis in the adjacent overlying sediments, that is, the production of large quantities of free-base desoxophylloerythroetioporphyrin (DPEP) occurred in a section (477-7-5) presently only 49.8 meters sub-bottom. Present depth and age of these sediments are such that only chlorins and phorbides would be expected.Carotenoid (i.e., tetraterpenoids) concentrations were found to decrease rapidly with increasing sub-bottom depth. Less deeply buried sediments (e.g., 0-30 m) yielded mixtures of carotenes and oxygen-substituted carotenoids. Oxygencontaining (oxy-, oxo-, epoxy-) carotenoids were found to be lost preferentially with increased depth of burial.Early carotenoid diagenesis is suggested as involving interacting reductions and dehydrations whereby dehydro-, didehydro-, and retro-carotenes are generated. Destruction of carotenoids as pigments may involve oxidative cleavage of the isoprenoid chain through epoxy intermediates, akin to changes in the senescent cells of plants.Perylene was found to be a common component of the extractable organic matter from all sediments investigated. The generation of alkyl perylenes was found to parallel increases in the existing thermal regime at all sites. Igneous sills and sill complexes within the sediment profile of Site 481 altered (i.e., scrambled) the otherwise straightforward thermally induced alkylation of perylene.The degree of perylene alkylation is proposed as an indicator of geothermal stress for non-contemporaneous marine sediments.

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Section: Apo-carotenoids Refers To Tentatively Identified Apo-carotenmentioning

confidence: 98%

“…Re-equilibration of the column, following a 20% methanol in acetone flush, for periods of 20 to 30 minutes also enhanced separation of the hydrocarbon pigments (cf. Hajibrahim et al, 1978).…”

Section: Pigment Yield and Observed Trendsmentioning

confidence: 99%

Geochemistry of Tetrapyrrole, Tetraterpenoid, and Perylene Pigments in Sediments from the Gulf of California: Deep Sea Drilling Project Leg 64, Sites 474, 477, 479, and 481, and Scripps Institution of Oceanography Guaymas Basin Survey Cruise Leg 3, Sites 10G and 18G

Baker¹,

Louda²

1982

Initial Reports of the Deep Sea Drilling Project, 64

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“…Until recently, the complexity of these mixtures outstripped the techniques available for separation, precluding analysis of all but major pigments (Fox, 1937;Fox et al, 1945; Carotenoids characteristic of specific classes of organisms have now been used to identify sources of sedimentary organic matter Hajibrahim et al, 1978, Cardoso et al, 1978Griffiths et al, 1978), deduce transformation pathways (Repeta and Gagosian, 1982 a,b), recognize pollution events (Griffiths and Edmondson, 1975;Griffiths et al, 1969), and monitor eutrophication in Lake Zurich (Zullig, 1981).…”

Section: Introductionmentioning

confidence: 99%

“…There are numerous reports of HPLC separations of marine carotenoids (Stewart and Wheaton, 1971;Cadosch and Euguster 1974;Eskins et al, 1977;Fiksdahl et al, 1978;Hajibrahim et al, 1978;Vecchi and Muller, 1979;Ohmacht, 1979;Eskins and Dutton, 1979;Paankker and Gallegraeff, 1979;Ronneberg et al, 1980;Davies and Holdsworth 1980;Schiedt et al, 1981). Schwartz and Von Elbe (1982) have reviewed HPLC analysis of plant pigments, and systematic studies of a wide variety of carotenes and xanthophylls have been reported by Fiksdahl et al, (1978) and Matus et al, (1981).…”

Section: Introductionmentioning

confidence: 99%

Transformations of carotenoids in the oceanic water column

Repeta¹

1982

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In an effort to understand the more general mechanisms and rates of pre-depositional reactions that transform organic matter, the types and relevant time scales of reactions that transform carotenoid pigments in the oceanic water column were studied.In the present study, a model was constructed for organic matter cycling that consisted of three parts: 1) the synthesis of carotenoid pigments by phytoplankton in the euphotic zone, 2) consumption and metabolism of some fraction of these pigments by heterotrophic organisms, and 3) removal of metabolic by-products to the sediments by large particle (e.g. fecal pellet) transport. The model separates particlate matter into reservoirs according to the degradation processes that have occurred since synthesis. The goal is to sample these particulate reservoirs, determine the compositional differences between them, and construct a mechanistic pathway for the transformations that occur as material is transferred between reservoirs.Suspended particulate matter collected in the surface waters of Buzzards Bay, Massachusetts and the Peru upwelling region has a carotenoid distribution reflecting the phytoplanktonic source of the material. The carotenoid distribution of sediment trap samples collected in these areas was dominated by transformation products. Fucoxanthin, the primary carotenoid of marine diatoms, typically constituted 77-100% of the total fucopigments in suspended particulate matter. In sediment trap samples this pigment constituted only 4-85% of the total. The remaining 15-96% of the pigments consisted of the fucoxanthin transformation products: free alcohols (2-94%), dehydrates (0-6%), and opened epoxides (0-19%).Postulated transformation products were synthesized to determine the structure of isolated compounds. Simultaneously, iodine catalyzed photoisomerization of fucopigments was tested as a potential method for the unambiguous identification of caotenoids requiring only the nanogram amounts of material typically found in samples.Preliminary results suggest that carotenoid esters are hydrolyzed at a rate determined by the turnover of primary productivity. The dehydrated and epoxide opened degradation products of fucoxanthin represent products of transformation reactions that operate over much longer time scales (0.1-10 yr). Dehydration and epoxide opening are not significant water column transformations, but are important in surface sediments. A trans-3 formation pathway of ester hydrolysis + dehydration + epoxide opening + further dehydration is proposed for fucoxanthin. Preliminary evidence for a parallel transformation squence for structurally similar carotenoids is also presented.

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“…Normal phase HPLC was carried out based on a system reported by Hajibrahim et al (1978). Separations were made on a silica column (Partisil5 pm irregular) using a concave gradient (curve 7 on the Waters 720 programme) of acetone (2-75%) in hexane for 30 minutes at 1 ml/min.…”

Section: Analysis By Hplcmentioning

confidence: 99%

Possible Origins of a Novel Carotenoid in Sediments from two Organic-rich Sites

Ridout

Morris

Tibbetts³

1986

Chemistry and Ecology

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Samples of Recent sediment taken from box core samples from the Peru Continental Shelf (12"01.8'S; 77"29.3'W) and the Namibian Shelf (22'35.0s 13"45.0'E) were examined for pigments. Two 'novel' carotenoids, previously reported from the Namibian Shelf were identified, one (Peru 2/Walvis 2) as a major component at both sites. The sediments at these sites represent organic-rich diatomaceous oozes formed as a result of high primary productivity.Comparison of the sediment chemistry of the sites suggests that the novel carotenoid Peru 2/Walvis 2 may have its origin in a previously uncharacterised biological source, although the possibility that it is a transformation product of fucoxanthin cannot be ruled out.

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Analysis of carotenoid and porphyrin pigments of geochemical interest by high-performance liquid chromatography

Abstract: High-performance liquid chromatography (HPLC) is shown to be a powerful tool in the analysis of carotenoid and porphyrin pigments. Columns packed with 5-µ irregular silica gel

Cited by 83 publications

References 8 publications

Geochemistry of Tetrapyrrole, Tetraterpenoid, and Perylene Pigments in Sediments from the Gulf of California: Deep Sea Drilling Project Leg 64, Sites 474, 477, 479, and 481, and Scripps Institution of Oceanography Guaymas Basin Survey Cruise Leg 3, Sites 10G and 18G

Geochemistry of Tetrapyrrole, Tetraterpenoid, and Perylene Pigments in Sediments from the Gulf of California: Deep Sea Drilling Project Leg 64, Sites 474, 477, 479, and 481, and Scripps Institution of Oceanography Guaymas Basin Survey Cruise Leg 3, Sites 10G and 18G

Transformations of carotenoids in the oceanic water column

Possible Origins of a Novel Carotenoid in Sediments from two Organic-rich Sites

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