Bacteriohopanepolyol data of sediment cores GeoB3918-2 and GeoB1514-6 from the Amazon River

We have investigated the delivery of terrestrial organic carbon (OC) to the Amazon shelf and deep sea fan based on soil marker bacteriohopanepolyols (BHPs; adenosylhopane and related compounds) and branched glycerol dialkyl glycerol tetraethers (GDGTs), as well as on 14C dating of bulk organic matter. The microbial biomarker records show persistent burial of terrestrial OC, evidenced by almost constant and high BIT values (0.6) and soil marker BHP concentration [80-230 µg/g TOC (total OC)] on the late Holocene shelf and even higher BIT values (0.8-0.9), but lower and more variable soil-marker BHP concentration (40-100 µg/g TOC), on the past glacial deep sea fan. Radiocarbon data show that OC on the shelf is 3-4 kyr older than corresponding bivalve shells, emphasizing the presence of old carbon in this setting. We observe comparable and unexpectedly invariant BHP composition in both marine sediment records, with a remarkably high relative abundance of C-35 amino BHPs including compounds specific for aerobic methane oxidation on the shelf (avg. 50% of all BHPs) and the fan (avg. 40%). Notably, these marine BHP signatures are strikingly similar to those of a methane-producing floodplain area in one of the Amazonian wetland (várzea) regions. The observation indicates that BHPs in the marine sediments may have initially been produced within wetland regions of the Amazon basin and may therefore document persistent export from terrestrial wetland regions, with subsequent re-working in the marine environment, both during recent and past glacial climate conditions.

Organic carbon and carbohydrates in waters of the Amazon River, Atlantic Ocean, and Tropical Indian Ocean

A method is presented to study carbohydrate composition of marine objects involved into sedimento- and diagenesis (plankton, particulate matter, benthos, and bottom sediments). Analysis of the carbohydrates is based on consecutive separation of their fractions with different solvents (water, alkali, and acid). Ratios of carbohydrate fractions allows to evaluate lability of carbohydrate complexes. They are also usable as an indicators of biogeochemical processes in the ocean, as well of genesis and degree of transformation of organic matter in bottom sediments and nodules. Similarity in monosaccharide composition is shown for dissolved organic matter and aqueous and alkaline fractions of seston and particulate matter.

Terrigenous biomarker proxies analysed in the Amazon River system

Paleoenvironmental studies based on terrigenous biomarker proxies from sediment cores collected close to the mouth of large river systems rely on a proper understanding of the processes controlling origin, transport and deposition of biomarkers. Here, we contribute to the understanding of these processes by analyzing long-chain n-alkanes from the Amazon River system. We use the dD composition of long-chain n-alkanes from river bed sediments from the Amazon River and its major tributaries, as well as marine core-top samples collected off northeastern South America as tracers for different source areas. The d13C composition of the same compounds is used to differentiate between long-chain n-alkanes from modern forest vegetation and petrogenic organic matter. Our d13C results show depleted d13C values (-33 to -36 per mil) in most samples, indicating a modern forest source for most of the samples. Enriched values (-31 to -33 per mil) are only found in a few samples poor in organic carbon indicating minor contributions from a fossil petrogenic source. Long-chain n-alkane dD analyses show more depleted values for the western tributaries, the Madeira and Solimões Rivers (-152 to -168 per mil), while n-alkanes from the lowland tributaries, the Negro, Xingu and Tocantins Rivers (-142 to -154 per mil), yield more enriched values. The n-alkane dD values thus reflect the mean annual isotopic composition of precipitation, which is most deuterium-depleted in the western Amazon Basin and more enriched in the eastern sector of the basin. Samples from the Amazon estuary show a mixed long-chain n-alkane dD signal from both eastern lowland and western tributaries. Marine core-top samples underlying the Amazon freshwater plume yield dD values similar to those from the Amazon estuary, while core-top samples from outside the plume showed more enriched values. Although the variability in the river bed data precludes quantitative assessment of relative contributions, our results indicate that long-chain n-alkanes from the Amazon estuary and plume represent an integrated signal of different regions of the onshore basin. Our results also imply that n-alkanes are not extensively remineralized during transport and that the signal at the Amazon estuary and plume includes refractory compounds derived from the western sector of the Basin. These findings will aid in the interpretation of plant wax-based records of marine sediment cores collected from the adjacent ocean.

Non-indigenous species in the North and Baltic Seas and the Great Lakes-St. Lawrence River region

List of non-indigenous species (NIS) established in the Great Lakes-St. Lawrence River region and the North and Baltic Seas region, their geographic origin, and taxonomic assignment. Asterisks mark the NIS that occur in both the North and Baltic Seas and the Great Lakes-St. Lawrence River regions. GL, SL, NW, NE, SW and SE denote the Great Lakes, St. Lawrence River, north-west, north-east, south-west, and south-east, respectively. Eurasia represents inland freshwaters except Yangtze River, Indo-Pacific represents Indian Ocean and the archipelago of Indonesia, Malaysia, and Pilipinas, North America (N America) represents inland freshwaters except the Laurentian Great Lakes, St. Lawrence and Mississippi Rivers, while Australia, New Zealand, Africa and South America (S America) cover all inland freshwaters in these areas.

Heterocyst glycolipids in surface sediments and water samples of the Amazon shelf

Marine endosymbiotic heterocystous cyanobacteria make unique heterocyst glycolipids (HGs) containing pentose (C5) moieties. Functionally similar HGs with hexose (C6) moieties found in free-living cyanobacteria occur in the sedimentary record, but C5 HGs have not been documented in the natural environment. Here we developed a high performance liquid chromatography multiple reaction monitoring (MRM) mass spectrometry (HPLC-MS2) method specific for trace analysis of long chain C5HGs and applied it to cultures of Rhizosolenia clevei Ostenfeld and its symbiont Richelia intracellularis which were found to contain C5 HGs and no C6 HGs. The method was then applied to suspended particulate matter (SPM) and surface sediment from the Amazon plume region known to harbor marine diatoms carrying heterocystous cyanobacteria as endosymbionts. C5 HGs were detected in both marine SPM and surface sediments, but not in SPM or surface sediment from freshwater settings in the Amazon basin. Rather, the latter contained C6 HGs, established biomarkers for free-living heterocystous cyanobacteria. Our results indicate that the C5 HGs may be potential biomarkers for marine endosymbiotic heterocystous cyanobacteria.

Accumulation and composition of terrigenous material on Ceara rise over the past 55 Ma

Ceara Rise, located east the Amazon River mouth, is covered with a thick blanket of pelagic carbonate and hemipelagic terrigenous sediment. The terrigenous component has been extracted from 57 bulk sediment samples at Ocean Drilling Program (ODP) Sites 925 and 929 on Ceara Rise to obtain a Cenozoic record of riverine discharge from northern South America. From the early Eocene to early Miocene (55-20 Ma), terrigenous accumulation was dominated by moderate amounts of generally large-grained, gray to green sediment especially depleted in elements that are enriched in post-Archaean shale (e.g. Cs, Th, Yb). However, pulsed inputs of relatively small-grained, gray to green terrigenous sediment less depleted in the above elements occurred in the late Eocene and Oligocene. The accumulation of terrigenous sediment decreased significantly until 16.5 Ma. In the middle Miocene (16.5-13 Ma), terrigenous accumulation was dominated by small amounts of small-grained, tan sediment notably depleted in Na and heavy rare earth elements. The accumulation rate of terrigenous sediment increased markedly from the latest Miocene (10 Ma) to the present day, a change characterized by deposition of gray-green sediment enriched in elements that are enriched in post-Archaean shale. Observed changes in terrigenous sediment at Ceara Rise record tectonism and erosion in northern South America. The Brazil and Guyana shields supplied sediment to the eastern South American margin until the middle Miocene (20-16.5 Ma) when a period of thrusting, shortening and uplift changed the source region, probably first to highly weathered and proximal Phanerozoic sediments. By the late Miocene (9 Ma), there was a transcontinental connection between the Andes and eastern South America. Weathering products derived from the Andes have increasingly dominated terrigenous deposition at Ceara Rise since the Late Miocene and especially since the late Pliocene.

Comparison of glacial/interglacial carbonate concentrations in Atlantic sediments

To assess the regional effects of glaciation on sedimentation in the Atlantic Ocean we compare sediment types, distributions, and rates between Recent (core top) and last glacial maximum (LGM: ~18,000 years B.P.) stratigraphic levels. Based upon smear slides and carbonate analyses in 178 cores we find that glacial age carbonate content is generally lower than Recent. During both the Recent and LGM, carbonate content shows an east/west asymmetry with western basins exhibiting lower carbonate values. Input of ice-rafted detritus into the North Atlantic during LGM time interrupts this topographic control on carbonate distribution considerably farther south than at present; in the South Atlantic this effect is minor. Comparison of LGM and Recent sediment distributions indicates that the LGM seafloor was dominated by biogenic oozes, calcareous clays, and clays, while the Recent is dominated by biogenic oozes and marls. Coarse-grained detritus is much more prevalent in LGM sediments, derived not only from glacial input but also from fluvial and aeolian sources. Sedimentation rates, calculated from LGM to Recent sediment thickness in cores, are <4 cm/1000 yr for most of the ocean. Higher rates are typical of the continental margin off the Amazon River, the North American Basin, and a small region off west equatorial Africa.

Long chain diols and diol indices of surface sediments of the Iberian Atlantic margin

Long chain diols are lipids that have gained interest over the last years due to their high potential to serve as biomarkers and diol indices have been proposed to reconstruct upwelling conditions and sea surface temperature (SST). However, little is known about the sources of the diols and the mechanisms impacting their distribution. Here we studied the factors controlling diol distributions in the Iberian Atlantic margin, which is characterized by a dynamic continental shelf under the influence of upwelling of nutrient-rich cold deep waters, and fluvial input. We analyzed suspended particulate matter (SPM) of the Tagus river, marine SPM and marine surface sediments along five transects off the Iberian margin, as well as riverbank sediments and soil from the catchment area of the Tagus river. Relatively high fractional abundances of the C32 1,15-diol (normalized with respect to the 1,13- and 1,15-diols) were observed in surface sediments in front of major river mouths and this abundance correlates strongly with the BIT index, a tracer for continental input of organic carbon. Together with an even higher fractional abundance of the C32 1,15-diol in the Tagus river SPM, and the absence of long chain diols in the watershed riverbank sediments and soils, we suggest that this long chain diol is produced in-situ in the river. Further support for this hypothesis comes from the small but distinct stable carbon isotopic difference of 1.3? with the marine C28 1,13-diol. The 1,14-diols are relatively abundant in surface sediments directly along the northern part of the coast, close to the upwelling zone, suggesting that Diol Indices based on 1,14-diols would work well as upwelling tracers in this region. Strikingly, we observed a significant difference in stable carbon isotopic composition between the monounsaturated C30:1 1,14- and the saturated C28 1,14-diol (3.8±0.7 per mil), suggesting different sources, in accordance with their different distributions. In addition, the Long chain Diol Index (LDI), a proxy for sea surface temperature, was applied for the surface sediments. The results correlate well with satellite SSTs offshore but reveal a significant discrepancy with satellite-derived SSTs in front of the Tagus and Sado rivers. This suggests that river outflow might compromise the applicability of this proxy.

Tab. 1: Trace-element concentrations in ore samples collected from mercury mines and deposits in southwestern Alaska

A belt of small but numerous mercury deposits extends for about 500 km in the Kuskokwim River region of southwestern Alaska. The southwestern Alaska mercury belt is part of widespread mercury deposits of the circum Pacific region that are similar to other mercury deposits throughout the world because they are epithermal with formation temperatures of about 200 °C, the ore is dominantly cinnabar with Hg-Sb-As±Au geochemistry, and mineralized forms include vein, vein breccias, stockworks, replacements, and disseminations. The southwestern Alaska mercury belt has produced about 1400 t of mercury, which is small on an international scale. However, additional mercury deposits are likely to be discovered because the terrain is topographically low with significant vegetation cover. Anomalous concentrations of gold in cinnabar ore suggest that gold deposits are possible in higher temperature environments below some of the Alaska mercury deposits. We correlate mineralization of the southwestern Alaska mercury deposits with Late Cretaceous and early Tertiary igneous activity. Our 40Ar/39Ar ages of 70 ±3 Ma from hydrothermal sericites in the mercury deposits indicate a temporal association of igneous activity and mineralization. Furthermore, we suggest that our geological ancl geochemical data from the mercury deposits indicate that ore fluids were generated primarily in surrounding sedimentary wall rocks when they were cut by Late Cretaceous and early Tertiary intrusions. In our ore genesis model, igneous activity provided the heat to initiate dehydration reactions and expel fluids from hydrous minerals and formational waters in the surrounding sedimentary wall rocks, causing thermal convection and hydrothermal fluid flow through permeable rocks and along fractures and faults. Our isotopic data from sulfide and alteration minerals of the mercury deposits indicate that ore fluids were derived from multiple sources, with most ore fluids originating from the sedimentary wall rocks.

Tab. 2: U-Pb ion-microprobe ages from Taymyr peninsula

We present the initial results of a U-Th-Pb zircon ion-microprobe investigation on samples from the Central Belt of Taimyr, in order to constrain its tectono-magmatic evolution. The zircon samples are from a deformed twomica granite (Faddey Massif), deformed metamorphosed gabbroic dike entrained as pods and lenses within metamorphosed tholeiitic basalts of the Kunar-Mod volcanic suite (Klyaz'ma River region), a metamorphosed rhyolite of the same volcanic suite overlying the basic metavolcanic rocks, as well as an undeformed dolerite dike which intrudes the metamorphosed Kunar-Mod basic volcanic rocks. Preliminary results on zircons from the two-mica granite suggest a crystallization age of ~630 Ma for this rock, with inheritance from assimilated crust 840 Ma to 1.1 Ga in age. In the Klyaz'ma River region, zircons from the meta-rhyolite yield a concordant age of -630 Ma. Zircons from the entrained metagabbroic dikes have so far yielded an age of -615 Ma (1 grain), as well as Archean ages (5 grains, concordant at 2.6-2.8 Ga). It seems likely that the Archean grains represent assimilation of older crustal material. Zircons from the post-tectonic dolerite dike have a bimodal age distribution. A well-defined younger age of 281 ±9 Ma is interpreted to represent the crystallization age of the dike, while older, concordant ages of 2.6-2.9 Ga likely represent assimilation of Archean crust (Siberian craton at depth). Several important conclusions can be drawn from the data. (1) The mafic and felsic lithologies of the Kunar-Mod volcanic suite are genetically related and should be the same age. Ages of-630 Ma (meta-rhyolite) and -615 Ma (metagabbroic dikes representing the latest stage of mafic magmatism associated the Kunar-Mod suite) suggest that these lithologies may be the same age, but more data are required to confirm this hypothesis. (2) The 630 Ma two-mica granite is similar in age to the time of high-grade metamorphism, suggesting that syntectonic granite emplacement accompanied obduction of the accretionary Central Belt to the Siberian craton. (3) An Early Permian age is well defined for the undeformed dolerite dike. Dolerite dikes occur across the whole of Taimyr, but are deformed to the south. If related, this single magmatic event pre-dates Permo-Triassic Siberian trap magmatism. Furthermore, it suggests that deformation was localized to southeastern Taimyr.

Age model, stable isotopes, major element proportions and endmember unmixing results from four western tropical Atlantic cores

We investigate changes in the delivery and oceanic transport of Amazon sediments related to terrestrial climate variations over the last 250 ka. We present high-resolution geochemical records from four marine sediment cores located between 5 and 12° N along the northern South American margin. The Amazon River is the sole source of terrigenous material for sites at 5 and 9° N, while the core at 12° N receives a mixture of Amazon and Orinoco detrital particles. Using an endmember unmixing model, we estimated the relative proportions of Amazon Andean material ("%-Andes", at 5 and 9° N) and of Amazon material ("%-Amazon", at 12° N) within the terrigenous fraction. The %-Andes and %-Amazon records exhibit significant precessional variations over the last 250 ka that are more pronounced during interglacials in comparison to glacial periods. High %-Andes values observed during periods of high austral summer insolation reflect the increased delivery of suspended sediments by Andean tributaries and enhanced Amazonian precipitation, in agreement with western Amazonian speleothem records. Increased Amazonian rainfall reflects the intensification of the South American monsoon in response to enhanced land-ocean thermal gradient and moisture convergence. However, low %-Amazon values obtained at 12° N during the same periods seem to contradict the increased delivery of Amazon sediments. We propose that reorganizations in surface ocean currents modulate the northwestward transport of Amazon material. In agreement with published records, the seasonal North Brazil Current retroflection is intensified (or prolonged in duration) during cold substages of the last 250 ka (which correspond to intervals of high DJF or low JJA insolation) and deflects eastward the Amazon sediment and freshwater plume.

Geological, geochemical and biogeochemical data on boundary zones of the Atlantic Ocean

Results of studies in two biogeochemically active zones of the Atlantic Ocean (the Benguela upwelling waters and the region influenced by the Congo River run-off) are reported in the book. A multidisciplinary approach included studies of the major elements of the ocean ecosystem: sea water, plankton, suspended matter, bottom sediments, interstitial waters, aerosols, as well as a wide complex of oceanographic studies carried out under a common program. Such an approach, as well as a use of new methodical solutions led to obtaining principally new information on different aspects of oceanology.