Correlation between geochemical environments and controlling factors in the metallation of porphyrins

Experimental study on metallation of tetrapyrroles in biphasic systems showed that complexation with metal cations of the first transition series is a feasible under chemical environments similar to the naturally occurring ones. The metal transport from the aqueous media to the organic, which is a novel approach using naturally occurring fatty acids hydroxy aromatic compounds and thiols, is demonstrated. Selectivity between Ni²⁺ and VO²⁺ complexation is achieved under sulfurous rich conditions. The kinetic implications are discussed in view of their geoenvironmental applicability.     

Iron porphyrins in the Permian Kupferschiefer of the lower Rhine Basin, N.W. Germany

Immature samples of the Permian Kupferschiefer from the Lower Rhine Basin in N.W. Germany were analysed for tetrapyrrole pigment type and abundance. The sediment, thought to have been deposited in a marine regime with enhanced salinity, was found to contain high concentrations of metalloporphyrins. The porphyrins are complexed to nickel (Ni) and oxovanadium (V=0), but high abundances of iron (Fe) porphyrins were also detected using UV/visible spectroscopy and mass spectrometry. The presence in the latter of series of aetioporphyrins, cycloalkanoporphyrins, di-cycloalkanoporphyrins and benz-cycloalkanoporphyrins was confirmed by accurate mass measurements; HPLC co-injection of deoxophylloerythroetioporphyrin (C₃₂ DPEP) with the demetallated iron porphyrins indicated its presence in the sediment as an iron complex. The study provides the first evidence for the occurrence of Fe porphyrins in geological samples other than coals and lignites, and reports the highest concentrations in sedimentary organic matter to date.     

Profiles of Fecal Porphyrins in River Otters Following the Exxon Valdez Oil Spill

Median levels of Coproporphyrin III (Copro III) in fecal samples of river otters (Lontra canadensis) collected from an oiled area in Prince William Sound, Alaska, USA, during 1990 were significantly higher than in samples collected from the same oiled area during 1996 (p=0.011, one way analysis of variance), a nonoiled reference area in Prince William Sound during 1996 (p=0.002) and a reference area in southeast Alaska during 1998 (p=0.004). An overall test of significance that combined probabilities from the statistical analysis of this porphyrin study with those from other biomarker studies revealed a significant difference in physiological response of river otters between oiled and nonoiled areas of the Sound for 1990 (p < 0.01). We demonstrated that changes in levels of fecal porphyrins may serve as a biomarker that may contribute to a health assessment of wild river otters.     

Multimolecular data processing and display in organic geochemistry: The evaluation of petroporphyrin GC-MS data

A novel method for handling and presenting multimolecular abundance data, derived from gas chromatographic-mass spectrometric analyses (GC-MS), is introduced. The method facilitates carbon number labeling of compounds, specifically in the case of porphyrins, by means of a porphyrin-index, which is part of a novel identification code for porphyrins. Identification code, relative abundance and structure information of each compound recognised are stored in a database, which affords a variety of characteristic displays and tables upon manipulation. The combined facilities allow the direct comparison of samples of different origin, maturity and/or palaeoenvironment. Correlation studies, such as oil/oil or oil/source rock, are also facilitated by comparison of characteristic “fingerprint” histogram patterns. The ability of the method is exemplified through analysis of the porphyrin distributions of Boscan oil, La Luna shale, Gilsonite bitumen and Serpiano shale.     

Porphyrin geochemistry of Atlantic Jurassic-Cretaceous black shales

Late Jurassic-early Cretaceous black shales and an overlying sequence of Albian-Campanian zeolitic claystones from the Falkland Plateau (DSDP/IPOD Leg 71, Site 511) were analyzed for tetrapyrrole pigment type and abundance. The “black shale” sequence was found to be rich in DPEP-series dominated free-base, nickel (Ni) and, to a lesser extent, vanadyl (V = 0) porphyrins. A low level of organic maturity (i.e. precatagenesis) is indicated for these strata as nickel chelation by free-base porphyrins is only 50–75% complete, proceeding down-hole to 627 meters sub-bottom. Electronic and mass spectral data reveal that the proposed benzo-DPEP (BD) and tetrahydrobenzo-DPEP (THBD) series are present in the free-base and Ni species, as well as the more usual occurrence in V = 0 porphyrin arrays. Highly reducing conditions are suggested by an abundance of the PAH perylene, substantial amounts of the THBD/BD series and a redox equilibrium between free-base DPEP and 7,8-dihydro-DPEP series, which exist in a 7:1 molar ratio. The Albian-Campanian claystone strata were found to be tetrapyrrolepoor, and those pigments present were typed as Cu/Ni highly dealkylated (C₂₆ max.) etioporphyrins, thought to be derived via redeposition and oxidation of terrestrial organic matter (OM). Results from the present study are correlated to our past analyses of Jurassic-Cretaceous sediments from Atlantic margins in an effort to relate tetrapyrrole quality and quantity to basin evolution and OM sources in the proto-Atlantic.     

Analysis of chlorophyll diagenesis—II. Solvent effects on metal incorporation into chlorophyll diagenetic products

We are attempting to quantify selected transitions in the diagenetic pathway of chlorophyll in deep ocean sediments. To analyze the aromatization from phorbides (less stable) to porphyrins (more stable), we used a model system which closely resembles the compounds identified in oceanic sediments. Kinetic parameters were determined for the incorporation of copper into deoxomesopyropheophorbide a methyl ester (DOMPP) and deoxophylloerythrin methyl ester (DPE) in a series of solvents ranging from highly polar and protic to non-polar and aprotic, representing varying sedimentary environments. In the reaction of copper with these two compounds, the activation parameters for the reaction with DOMPP indicate that DOMPP is more sensitive to the environment than DPE. Also, over the temperature range studied, DOMPP always reacted faster than DPE under similar conditions. These two observations lend support to our previous hypothesis that the phorbide to porphyrin transition includes the metallophorbide as a short-lived intermediate in the reaction sequence.     

卟啉的研究现状及其应用

在前人研究资料及作者近年来的研究成果的基础上，综述了卟啉化合物地球化学研究的现状，包括金属卟啉的类型，卟啉的化学结构系列，高度脱链基卟啉和高碳数咔琳等及其它们在沉积物(如油页岩、煤和现代沉积物)中的分布特征和成因机理。指出了今后需要加强研究的领域，如沉积物中新的金属卟啉类型探讨和卟啉化学结构的确定等。文章还综述了卟啉化合物地球化学指标在地质勘探中的应用，如:评价生油岩质量，油源对比，油气运移研究，古沉积环境研究和有机质热成熟度研究等。     

Porphyrins in coal

The background to recent developments in investigations on coal porphyrins is reviewed. Essentially all the work of the past ten years has been with lignites and coals of the humic series. The concentrations of porphyrins and metalloporphyrins are low (0-ca. 10 μg g⁻¹), which makes for difficulties in isolation and analysis.The preferred methods of isolation and analysis are summarised. The coal porphyrins differ from the porphyrins from crude oil, oil shale and related deposits in a variety of ways which are discussed. The major differences are the predominance of the etio series over the cycloetio series (DPEP series), the presence of Fe and Ga porphyrins (rather than Ni and VO porphyrins), and the presence of mesoporphyrin IX in lignite.Recent results tend to support Treibs' original idea (1935) that, for the coal porphyrins, both chlorophyll and iron porphyrin (haem) sources are important. The application of a weighted mean molecular mass of the porphyrins present as a biological marker in determining coal rank (Porphyrin Index of Coalification) is illustrated. Current activity is directed to the isolation and identification of individual iron complexes, and here a combination of thin layer chromatography and paramagnetically shifted ¹H-NMR spectroscopy (of dicyanoferrihaems), together with direct comparison with authentic haems especially synthesised for the purpose, has been rewarding.     

Geochemical characterization of Malm Zeta laminated carbonates from the Franconian Alb, SW-Germany (II)

During Jurassic times, especially within the Malm ζ stage, local depressions formed on the Eastern Bavarian Carbonate Platform that were surrounded by wall reefs. This created a unique depositional environment, where in an open-marine setting stagnant and anoxic bottom waters developed in an intra-reef depression. Anoxic conditions were stabilized below wave base by enhanced salinity in the bottom waters and establishment of a density stratification. Biomarker analysis was applied to characterize palaeosalinity and redox conditions, utilizing organic sulfur compound, methylated chroman, hopanoid and saturated isoprenoid distributions. Prevention of terrigenous influx by protecting reef walls lead to iron deficiency in intra-reefal sediments causing early diagenetic sulfurization of functionalized lipids. Absence of clay-mineral catalysts and early sulfurization favored an unusual steroid distribution lacking rearranged analogues but providing coexistence of saturated steranes with βαα-, ααα- and αββ-configuration, Δ¹³⁽¹⁷⁾-spirosterenes, unknown sterenes and steradienes as well as mono-, di- and triaromatic steroids. Desulfurization of the polar fraction was carried out for two samples to verify that palaeoenvironment reconstruction based on free hydrocarbon and heterocompound distribution was not invalidated by sulfur quenching of selected compounds. Gammacerane was found to be the only component to occur exclusively in the sulfur-bound fraction. Only minor amounts of hydrocarbons were released upon desulfurization implying that free bitumen analysis was applicable for organofacies characterization. Organic petrological investigation of organic mats revealed the presence of two different types of such structures. Comparison of organoclast fluorescence spectra with those of extracted porphyrin fractions indicate an origin of porphyrins exclusively from cyanobacterial mats whereas algal dominated mats yield no porphyrins. This aims towards a better localization of specific biomarker origin in geological samples.