Geochemistry of tetrapyrrole, tetraterpenoid, and perylene pigments in sediments from the Gulf of California

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 Baker and Palmer, 1978; 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-p6. 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.

Chemistry of primary and secondary phases in intraplate basalts and volcaniclastic sediments at DSDP Leg 89 Holes

Electron microprobe data are presented for clinopyroxenes, plagioclases, palagonites, smectites, celadonites, and zeolites in Hole 462A sheet-flow basalts and Site 585 volcaniclastic sediments. Glomerocrystic clinopyroxenes in Hole 462A are predominantly Ti-poor augites with minor fractionation to ferroaugites in rim portions. Quenched plumose clinopyroxenes show considerable variation from Ca-rich to Ca-poor augites, although all are characterized by being Tirich and Cr-poor relative to the glomerocrysts. Two differentiated series of Site 585 pyroxene compositions, calcic augite and diopside-salite, demonstrate the coexistence, in the vitric and lithic clasts, of tholeiitic and alkali basalt types, respectively. Plagioclase compositions in all samples are mainly labradorites, although some zoned Hole 462A glomerocrysts range from An73 to An20 and are characterized by high Mg and Fe contents in the more calcic varieties. The K content of the plagioclases is highest in the more sodic crystals, although the overall higher orthoclase component of Site 585 plagioclases reflects the generally higher bulk-rock K content. The compositions of both secondary smectites and celadonites are similar irrespective of the alteration location (glass, matrix, vesicles, etc.), although brown smectites replacing interstitial glass have marginally higher total Fe contents than pale green and yellow smectites. Analyzed zeolites are mainly phillipsites with variable alkali content, and, together with associated celadonite, represent late-stage alteration repositories for K under mildly oxidizing conditions. The compositions of both early and late secondary minerals are typical of those formed by the submarine alteration of basaltic rocks at low temperatures.