A relationship between aerosol transport and compound-specific d13C land plant biomarker and pollen records

We examined near-surface, late Holocene deep-sea sediments at nine sites on a north-south transect from the Congo Fan (4°S) to the Cape Basin (30°S) along the Southwest African continental margin. Contents, distribution patterns and molecular stable carbon isotope signatures of long-chain n-alkanes (C27-C33) and n-alkanols (C22-C32) are indicators of land plant vegetation of different biosynthetic types, which can be correlated with concentrations and distributions of pollen taxa in the same sediments. Calculated clusters of wind trajectories and satellite Aerosol Index imagery afford information on the source areas for the lipids and pollen on land and their transport pathways to the ocean sites. This multidisciplinary approach on an almost continental scale provides clear evidence of latitudinal differences in lipid and pollen composition paralleling the major phytogeographic zonations on the adjacent continent. Dust and smoke aerosols are mainly derived from the western and central South African hinterland dominated by deserts, semi-deserts and savannah regions rich in C4 and CAM plants. The northern sites (Congo Fan area and northern Angola Basin), which get most of their terrestrial material from the Congo Basin and the Angolan highlands, may also receive some material from the Chad region. Very little aerosol from the African continent is transported to the most southerly sites in the Cape Basin. As can be expected from the present position of the phytogeographic zones, the carbon isotopic signatures of the n-alkanes and n-alkanols both become isotopically more enriched in 13C from north to south. The results of the study suggest that this combination of pollen data and compound-specific isotope geochemical proxies can be effectively applied in the reconstruction of past continental phytogeographic developments.

Biomarkers, stable carbon isotope record and pollen distribution of the soutwest African continental margin

This is part 2 of a study examining southwest African continental margin sediments from nine sites on a north-south transect from the Congo Fan (4°S) to the Cape Basin (30°S) representing two glacial (MIS 2 and 6a) and two interglacial stages (MIS 1 and 5e). Contents, distribution patterns, and molecular stable carbon isotope signatures of long-chain n-alkanes (C27-C33) and n-alkanols (C22-C32) as indicators of land plant vegetation of different biosynthetic types were correlated with concentrations and distributions of pollen taxa in sediments of the same time horizons. Selected single pollen type data reveal details of vegetation changes, but the overall picture is best illustrated by summing pollen known to predominantly derive from C4 plants or C4 plus CAM plants. The C4 plant signals in the biomarkers are recorded in the delta13C data and in the abundances of C31 and C33 n-alkanes, and the C32 n-alkanol. Calculated clusters of wind trajectories for austral summer and winter situations for the Holocene and the Last Glacial Maximum afford information on the source areas for the lipids and pollen and their transport pathways to the ocean. This multidisciplinary approach provides clear evidence of latitudinal differences in leaf wax lipid and pollen composition, with the Holocene sedimentary data paralleling the current major phytogeographic zonations. The northern sites (Congo Fan area and northern Angola Basin) get most of their terrestrial material from the Congo Basin and the Angolan highlands dominated by C3 plants. Airborne particulates derived from the western and central South African hinterland dominated by deserts, semideserts, and savannah regions are rich in organic matter from C4 plants. As can be expected from the present and glacial positions of the phytogeographic zones, the carbon isotopic signatures of n-alkanes and n-alkanols both become isotopically more enriched in 13C from north to south. In the northern part of the transect the relative importance of C4 plant indicators is higher during the glacials than in the interglacials, indicating a northward extension of arid zones favoring grass vegetation. In the south, where grass-rich vegetation merges into semidesert and desert, the difference in C4 plant indicators is small.

Sedimentary lipids and palynomorphs of sediment core ABC26 from the Eastern Mediterranean

Selective degradation of organic matter in sediments is important for reconstructing past environments and understanding the carbon cycle. Here, we report on compositional changes between and within lipid classes and kerogen types (represented by palynomorph groups) in relation to the organic matter flux to the sea floor and oxidation state of the sediments since the early Holocene for central Eastern Mediterranean site ABC26. This includes the initially oxic but nowadays anoxic presapropelic interval, the still unoxidised lower part of the organic rich S1 sapropel, its postdepositionally oxidised and nowadays organic-poor upper part as well as the overlying postsapropelic sediments which have always been oxic. A general ~ 2.3 times increase in terrestrial and marine input during sapropel formation is estimated on the basis of the total organic carbon (TOC), pollen, spore, dinoflagellate cyst, n-alkane, n-alkanol and n-alkanoic acid concentration changes in the unoxidised part of the sapropel. The long-chain alkenones, 1,15 diols and keto-ols, loliolides and sterols indicate that some plankton groups, notably dinoflagellates, may have increased much more. Apart from the terrestrial and surface water contributions to the sedimentary organic matter, anomalous distributions and preservation of some C23-C27 alkanes, alkanols and alkanoic acids have been observed, which are interpreted as a contribution by organisms living in situ. Comparison of the unoxidised S1 sapropel with the overlying oxidised sapropel and the organic matter concentration profiles in the oxidised postsapropelic sediments demonstrates strong and highly selective aerobic degradation of lipids and palynomorphs. There seems to be a fundamental difference in degradation kinetics between lipids and pollen which may be possibly related with the absence of sorptive preservation as a protective mechanism for palynomorph degradation. The n-alkanes, Impagidinium, and Nematosphaeropsis are clearly more resistant than TOC. The n-alkanols and n-carboxylic acids are about equally resistant whereas the pollen, all other dinoflagellate cysts and other lipids appear to degrade considerably faster, which questions the practice of normalising to TOC without taking diagenesis into account. Selective degradation also modifies the relative distributions within lipid classes, whereby the longer-chain alkanes, alcohols and fatty acids disappear faster than their shorter-chain equivalents. Accordingly, interpretation of lipid and palynomorph assemblages in terms of pre- or syndepositional environmental change should be done carefully when proper knowledge of the postdepositional preservation history is absent. Two lipid-based preservation proxies are tested the diol-keto-ol oxidation index based on the 1,15C30 diol and keto-ols (DOXI) and the alcohol preservation index (API) whereby the former seems to be the most promising.

Organic geochemistry of Cretaceous black shales

Organic-carbon-rich 'black shales' and adjacent organic-carbon-poor rocks from three different Cretaceous settings encountered during ODP Leg 103 have been studied by organic geochemical methods. Rock-Eval analysis, carbon isotope data, and lipid biomarkers show organic matter to contain varying proportions of marine and continental materials. In Hauterivian-Barremian organic-carbon-rich marlstone turbidites, large amounts of land-derived organic matter are found. Aptian-Albian black-colored shales are interspersed within green claystones, from which they differ by containing more marine organic matter. An abbreviated layer of black shale from the Cenomanian/Turonian boundary is dominated by well-preserved marine organic matter. Downslope transport and rapid reburial within a predominantly oxygenated deep-water setting created most of these examples of black shales, except for the Cenomanian-Turonian deposits in which deep-water anoxia may have been involved.

General descriptions, organic contents and geolipid ratios at DSDP Leg 72 Holes

Organic matter in sediments from Sites 515, 516, and 517 reflects a history of low marine productivity and of oxygenated bottom waters in the western South Atlantic since the Pliocene. Organic carbon contents are low, averaging 0.26% of sediment weight. Distributions of n-alkanes, n-alkanols, and n-alkanoic acids show evidence of microbial reworking, and n-alkanes contain important terrigenous contributions, presumably of eolian origin.

General descriptions, organic contents and ratios of geolipid components at DSDP Holes 75-530B and 75-532

Distributions of free and bound n-alkanes, n-alkanoic acids, and n-alkanols were determined in order to compare the character of organic matter contained in organic-carbon-rich sediments from two sites sampled by the hydraulic piston corer. Two diatomaceous debris-flow samples of Pleistocene age were obtained from Hole 530B in the Angola Basin. A sample of bioturbated Pleistocene diatomaceous clay and another of bioturbated late Miocene nannofossil clay were collected from Hole 532 on the Walvis Ridge. Geolipid distributions of all samples contain large terrigenous contributions and lesser amounts of marine components. Similarities in organic matter contents of Hole 530B and Hole 532 sediments suggest that a common depositional setting, probably on the Walvis Ridge, was the original source of these sediments through Quaternary, and possibly late Neogene, times and that downslope relocation of these biogenic deposits has frequently occurred.

Organic geochemical comparison of Cretaceous green and black claystones at DSDP Hole 75-530A

Three pairs of Upper Cretaceous black shales and adjacent green claystones from Hole 530A were analyzed to compare types and amounts of organic matter and lipids and to seek information about their environments of deposition. The organic-carbon-rich black shales have C/N ratios nearly seven times those of the organic-carbon-lean green claystones. The lipid content of organic matter in the black shales is about ten times less than in adjacent green layers. Organic matter in both types of rocks is thermally immature, and distributions of alkanoic acids, alkanols, sterols, and alkanes contain large amounts of terrigenous components. Pristane/phytane ratios of less than one suggest that younger Turonian sediments were laid down under anoxic conditions, but ratios greater than one suggest that older Turonian Cenomanian deposits accumulated in a more oxic environment. Closely bedded green and black layers have very similar types of lipid distributions and differ primarily in concentrations, although black shales contain somewhat larger amounts of terrigenous lipid components. Geochemical and stratigraphic evidence suggests much of the organic matter in these samples originated on the African continental margin and was transported to the Angola Basin by turbidity flow. Rapid reburial of organic-carbon-rich sediments led to formation of the black shales.

Description of sediments, epoch, calcium carbonate, orgnic carbon, geolipids and mass accumulation rate at DSDP Holes 92-597A, 92-600 and 92-601B

Low concentrations of organic carbon in slowly accumulating sediments from Sites 597, 600, and 601 reflect a history of low marine productivity in the subtropical South Pacific since late Oligocene times. The distributions of n-alkanes, n-alkanoic acids, and n-alkanols provide evidence of the microbial alteration of sediment organic matter. Landderived hydrocarbons, possibly from eolian transport, dominate n-alkane distributions in these samples.

Organic geochemistry from different DSDP Holes in the subtropical South Atlantic Ocean

Organic matter has been characterized in samples of Pleistocene, Pliocene, and Miocene sediments from seven Deep Sea Drilling Project sites in the subtropical South Atlantic Ocean. Organic carbon concentrations average 0.3% for most samples, and n-alkanoic acid, n-alkanol, and alkane biomarkers indicate extensive microbial reworking of organic matter in these organic-carbon-lean sediments. Samples from the easternmost parts of the South Atlantic contain an average of 4.1% organic carbon and reflect the high productivity associated with the Benguela Current. Lipid biomarkers show less microbial reworking in these sediments. Eolian transport of land-derived hydrocarbons is evident at most of these oceanic locations.

(Table 1) Lipid biomarkers in surface sediments from the Gulf of Genoa

A series of molecular organic markers were determined in surface sediments from the Gulf of Genoa (Ligurian Sea) in order to evaluate their potential for palaeo-environmental reconstructions. Allochthonous input can be characterized by the distributions of n-C29 and n-C31 alkanes, n-C26 and n-C28 alkanols and branched glycerol dialkyl glycerol tetraethers (GDGTs), whose concentrations are generally highest near the river mouths. In the open basin however, terrestrial n-alkanes and n-alkanols may have an additional, aeolian source. Autochthonous input is represented by crenarchaeol and isoprenoid GDGTs. Their concentrations are highest in the open basin showing the preference of Thaumarchaeota for oligotrophic waters. Indications of a significant degradation of sterols and C37 alkenones exclude these lipids as reliable productivity proxies. Using terrestrial and aquatic lipids as end-members allows estimating the percentage of terrestrial organic matter between 20% and 58% in the coastal area decreasing to 1 to 30% in the deep basin. The spatial distribution of sea surface temperature (SST) estimates using the alkenone-based UK'37 index is very similar to the autumnal (November) mean satellite-based SST distribution. Conversely, TEXH86-derived SST estimates are close to winter SSTs in the coastal area and summer SSTs in the open basin. This pattern reflects presumably a shift in the main production of Thaumarchaeota from the coastal area in winter to the open basin in summer. This study represents a major prerequisite for the future application of lipid biomarkers on sediment cores from the Gulf of Genoa.