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.

(Appendix A) Geochemical composition of snow and eolian mineral dust from Berkner Island ice sheet, Antarctica

The Sr and Nd isotopic composition of dust extracted from recent snow layers at the top of Berkner Island ice sheet (located within the Filchner-Ronne Ice Shelf at the southern end of the Weddell Sea) enables us, for the first time, to document dust provenance in Antarctica outside the East Antarctic Plateau (EAP) where all previous studies based on isotopic fingerprinting were carried out. Berkner dust displays an overall crust-like isotopic signature, characterized by more radiogenic 87Sr/86Sr and much less radiogenic 143Nd/144Nd compared to dust deposited on the EAP during glacial periods. Differences with EAP interglacial dust are not as marked but still significant, indicating that present-day Berkner dust provenance is distinct, at least to some extent, from that of the dust reaching the EAP. The fourteen snow-pit sub-seasonal samples that were obtained span a two-year period (2002-2003) and their dust Sr and Nd isotopic composition reveals that multiple sources are at play over a yearly time period. Southern South America, Patagonia in particular, likely accounts for part of the observed spring/summer dust deposition maxima, when isotopic composition is shifted towards 'younger' isotopic signatures. In the spring, possible additional inputs from Australian sources would also be supported by the data. Most of the year, however, the measured isotopic signatures would be best explained by a sustained background supply from putative local sources in East Antarctica, which carry old-crust-like isotopic fingerprints. Whether the restricted East Antarctic ice-free areas produce sufficient eolian material has yet to be substantiated however. The fact that large (> 5 µm) particles represent a significant fraction of the samples throughout the entire time-series supports scenarios that involve contributions from proximal sources, either in Patagonia and/or Antarctica (possibly including snow-free areas in the Antarctic Peninsula and other areas as well). This also indicates that additional dust transport, which does not reach the EAP, must occur at low-tropospheric levels to this coastal sector of Antarctica.

Calcareous nannofossils of ODP Hole 123-765C and DSDP Hole 27-261

Sediments from the Argo Abyssal Plain (AAP), northwest of Australia, are the oldest known from the Indian Ocean and were recovered from ODP Site 765 and DSDP Site 261. New biostratigraphic and sedimentologic data from these sites, as well as reinterpretations of earlier findings, indicate that basal sediments at both localities are of Late Jurassic age and delineate a history of starved sedimentation punctuated by periodic influx of calcareous pelagic turbidites. Biostratigraphy and correlation of Upper Jurassic-Lower Cretaceous sediments is based largely on calcareous nannofossils. Both sites yielded variably preserved nannofossil successions ranging from Tithonian to Hauterivian at Site 765 and Kimmeridgian to Hauterivian at Site 261. The nannofloras are comparable to those present in the European and Atlantic Boreal and Tethyan areas, but display important differences that reflect biogeographic differentiation. The Argo region is thought to have occupied a position at the southern limit of the Tethyan nannofloral realm, thus yielding both Tethyan and Austral biogeographic features. Sedimentary successions at the two sites are grossly similar, and differences largely reflect Site 765's greater proximity to the continental margin. Jurassic sediments were deposited at rates of about 2 m/m.y. near the carbonate compensation depth (CCD) and contain winnowed concentrations of inoceramid prisms and nannofossils, redeposited layers rich in calcispheres and calcisphere debris, manganese nodules, and volcanic detritus. Lower Cretaceous and all younger sediments accumulated below the CCD at rates that were highest (about 20 m/m.y.) during mid-Cretaceous and Neogene time. Background sediment in this interval is noncalcareous claystone; turbidites dominate the sequence and are thicker and coarser grained at Site 765. AAP turbidites consist mostly of calcareous and siliceous biogenic components and volcanogenic smectite clay; they were derived from relatively deep parts of the continental margin that lay below the photic zone, but above the CCD. The Jurassic-Lower Cretaceous section is about the same thickness across the AAP; turbidites in this interval appear to have had multiple sources along the Australian margin. The Upper Cretaceous-Cenozoic section, however, is three times thicker at Site 765 than at Site 261; turbidites in this interval were derived predominantly from the south. Patterns of sedimentation across the AAP have been influenced by shifts in sea level, the CCD, and configuration of the continental margin. Major pulses of calcareous turbidite deposition occurred during Valanginian, Aptian, and Neogene time-all periods of eustatic lowstands and depressed CCD levels. Sediment redeposited on the AAP has come largely from the Australian outer shelf, continental slope, or rise, rather than the continent itself. Most terrigenous detritus was trapped in epicontinental basins that have flanked northwestern Australia since the early Mesozoic.

Lead isotopes of feldspar in North Atlantic Ocean sediments

The provenance of ice-rafted debris (IRD) deposited in the North Atlantic before, during, and after Heinrich event 2 has been determined through measuring the lead isotopic composition of single feldspar grains and multiple-grain composites from the larger than 150-µm size fraction, from cores from the eastern and western North Atlantic and from the Labrador Sea. Single-grain analyses are used to identify the specific continental sources of the IRD, whereas composite samples are used to assess the relative IRD contributions from different sources. All single grains from Heinrich layer 2 (H 2) as well as H 2 composites plot along a correlation line on a 207Pb/204Pb versus 206Pb/204Pb diagram characteristic of the Churchill province of the Canadian shield. This is yet another strong piece of evidence that this Heinrich event was dominated by a massive iceberg discharge of the Laurentide ice sheet lobe located over Hudson Bay. In contrast, single grains from the ambient glacial sediment (above and below H 2) have multiple sources: many of them also lie along the correlation line with H 2 grains, but many others have Pb signatures consistent with derivation from the Grenville province and the Appalachian range in North America and possibly from Scandinavia and Greenland. Composites from the ambient sediment generally lie well to the right of the H 2 reference line in agreement with the results of the single-grain analyses. The evidence provided by lead isotopes regarding the dominant role played by the Hudson Bay lobe of the Laurentide ice sheet in the development of the Heinrich events lends support to the binge/purge model advanced by MacAyeal [1993a, b] that invokes trapping of geothermal heat by the base of the icecap and subsequent basal melting as the mechanism that triggered the Heinrich events.

Mean chemical characteristics and volcano signatures of ice cores from Belukha, the Everest and three Svalbard sites

Ice cores from outside the Greenland and Antarctic ice sheets are difficult to date because of seasonal melting and multiple sources (terrestrial, marine, biogenic and anthropogenic) of sulfates deposited onto the ice. Here we present a method of volcanic sulfate extraction that relies on fitting sulfate profiles to other ion species measured along the cores in moving windows in log space. We verify the method with a well dated section of the Belukha ice core from central Eurasia. There are excellent matches to volcanoes in the preindustrial, and clear extraction of volcanic peaks in the post-1940 period when a simple method based on calcium as a proxy for terrestrial sulfate fails due to anthropogenic sulfate deposition. We then attempt to use the same statistical scheme to locate volcanic sulfate horizons within three ice cores from Svalbard and a core from Mount Everest. Volcanic sulfate is <5% of the sulfate budget in every core, and differences in eruption signals extracted reflect the large differences in environment between western, northern and central regions of Svalbard. The Lomonosovfonna and Vestfonna cores span about the last 1000 years, with good extraction of volcanic signals, while Holtedahlfonna which extends to about AD1700 appears to lack a clear record. The Mount Everest core allows clean volcanic signal extraction and the core extends back to about AD700, slightly older than a previous flow model has suggested. The method may thus be used to extract historical volcanic records from a more diverse geographical range than hitherto.

Eolian deposition on the Ontong Java Plateau

The record of eolian deposition on the Ontong Java Plateau (OJP) since the Oligocene (approximately 33 Ma) has been investigated using dust grain size, dust flux, and dust mineralogy, with the goal of interpreting the paleoclimatology and paleometeorology of the western equatorial Pacific. Studies of modern dust dispersal in the Pacific have indicated that the equatorial regions receive contributions from both the Northern Hemisphere westerly winds and the equatorial easterlies; limited meteorological data suggest that low-altitude westerlies could also transport dust to OJP from proximal sources in the western Pacific. Previous studies have established the characteristics of the grain-size, flux, and mineralogy records of dust deposited in the North Pacific by the mid-latitude westerlies and in the eastern equatorial Pacific by the low-latitude easterlies since the Oligocene. By comparing the OJP records with the well-defined records of the mid-latitude westerlies and the low-latitude easterlies, the importance of multiple sources of dust to OJP can be recognized. OJP dust is composed of quartz, illite, kaolinite/chlorite, plagioclase feldspar, smectite, and heulandite. Mineral abundance profiles and principal components analysis (PCA) of the mineral abundance data have been used to identify assemblages of minerals that covary through all or part of the OJP record. Abundances of quartz, illite, and kaolinite/chlorite covary throughout the interval studied, defining a mineralogical assemblage supplied from Asia. Some plagioclase and smectite were also supplied as part of this assemblage during the late Miocene and Pliocene/Pleistocene, but other source areas have supplied significant amounts of plagioclase, smectite, and heulandite to OJP since the Oligocene. OJP dust is generally coarser than dust deposited by the Northern Hemisphere westerlies or the equatorial easterlies, and it accumulates more rapidly by 1-2 orders of magnitude. These relationships indicate the importance of the local sources on dust deposition at OJP. The grain-size and flux records of OJP dust do not exhibit most of the events observed in the corresponding records of the Northern Hemisphere westerlies or the equatorial easterlies, because these features are masked by the mixing of dust from several sources at OJP. The abundance record of the Asian dust assemblage at OJP, however, does contain most of the features characteristic of dust flux by means of the Northern Hemisphere westerlies, indicating that the paleoclimatic and paleometeorologic signal of a particular source area and wind system can be preserved in areas well beyond the region dominated by that source and those winds. Identifying such a signal requires "unmixing" the various dust assemblages, which can be accomplished by combining grain-size, flux, and mineralogic data.

Rare earth elements from the Atlantic Sector

We present a Rare Earth Elements (REE) record at decadal resolution determined in the EPICA ice core drilled in Dronning Maud Land (EDML) in the Atlantic Sector of the East Antarctic Plateau, covering the transition from the last glacial age (LGA) to the early Holocene (26 600-7500 yr BP). Additionally, samples from potential source areas (PSAs) for Antarctic dust were analysed for their REE characteristics. The dust provenance is discussed by comparing the REE fingerprints in the ice core and the PSAs samples. We find a shift in REE composition at 15 200 yr BP in the ice core samples. Before 15 200 yr BP, the dust composition is very uniform and its provenance was likely to be dominated by a South American source. After 15 200 yr BP, multiple sources such as Australia and New Zealand become relatively more important, albeit South America is possibly still an important dust supplier. A similar change in the dust characteristics was observed in the EPICA Dome C ice core at around ~15 000 yr BP. A return to more glacial dust characteristics between ~8300 and ~7500 yr BP, as observed in the EPICA Dome C core, could not be observed in the EDML core. Consequently, the dust provenance at the two sites must have been different at that time.

Radiocarbon data, oxygen isotopic composition in foraminifera, freshwater diatoms data, and salinity estimations from ODP Holes 167-1019C and 167-1019D

Massive discharges of freshwater from the glacial lake Missoula to the northeast Pacific Ocean are thought to have sculpted the Channeled Scablands of eastern Washington and debouched via the Columbia River near 46°N. The dynamics and timing of these events and their impact on northeast Pacific circulation remain uncertain. Here we date marine records of anomalous freshwater inputs to the ocean based on freshwater diatoms, oxygen isotopes in foraminifera, and radiocarbon data. Low-salinity plumes from the Columbia River reduced sea-surface salinities by as much as 6 psu (practical salinity units) more than 400 km away between 16 and 31 cal (calendar) ka B.P. Anomalously high abundances of freshwater diatoms in marine sediments from the region precede generally accepted dates for the existence of glacial Lake Missoula, implying that large flooding or freshwater routing events were common during the advance of the Cordilleran Ice Sheet and that such events require multiple sources.

Magnetic extracts of three gravity cores located at the Ceará Rise, the Mid-Atlantic Ridge and the Sierra Leone Rise

The magnetic microparticle and nanoparticle inventories of marine sediments from equatorial Atlantic sites were investigated by scanning and transmission electron microscopy to classify all present detrital and authigenic magnetic mineral species and to investigate their regional distribution, origin, transport, and preservation. This information is used to establish source-to-sink relations and to constrain environmental magnetic proxy interpretations for this area. Magnetic extracts were prepared from sediments of three supralysoclinal open ocean gravity cores located at the Ceará Rise (GeoB 1523-1; 3°49.9'N/41°37.3'W), the Mid-Atlantic Ridge (GeoB 4313-2; 4°02.8'N/33°26.3'W), and the Sierra Leone Rise (GeoB 2910-1; 4°50.7'N/21°03.2'W). Sediments from two depths corresponding to marine isotope stages 4 and 5.5 were processed. This selection represents glacial and interglacial conditions of sedimentation for the western, central, and eastern equatorial Atlantic and avoids interferences from subsurface and anoxic processes. Crystallographic, elemental, morphological, and granulometric data of more than 2000 magnetic particles were collected by scanning and transmission electron microscopy. On basis of these properties, nine particle classes could be defined: detrital magnetite, titanomagnetite (fragmental and euhedral), titanomagnetite-hemoilmentite intergrowths, silicates with magnetic inclusions, microcrystalline hematite, magnetite spherules, bacterial magnetite, goethite needles, and nanoparticle clusters. Each class can be associated with fluvial, eolian, subaeric, and submarine volcanic, biogenic, or chemogenic sources. Large-scale sedimentation patterns are delineated as well: detrital magnetite is typical of Amazon discharge, fragmental titanomagnetite is a submarine weathering product of mid-ocean ridge basalts, and titanomagnetite-hemoilmenite intergrowths are common magnetic particles in West African dust. This clear regionalization underlines that magnetic petrology is an excellent indicator of source-to-sink relations. Hematite encrustations, magnetic spherules, and nanoparticle clusters were found at all investigated sites, while bacterial magnetite and authigenic hematite were only detected at the more oxic western site. At the eastern site, surface pits and crevices were seen on the crystal faces indicating subtle early diagenetic reductive dissolution. It was observed that paleoclimatic signatures of magnetogranulometric parameters such as the ratio of anhysteretic and isothermal remanent magnetizations can be formed either by mixing of multiple sources with separate, relatively narrow grain size ranges (western site) or by variable sorting of a single source with a broad grain size distribution (eastern site). Hematite, goethite, and possibly ferrihydrite nanoparticles occur in all sediment cores studied and have either high-coercive or superparamagnetic properties depending on their partly ultrafine grain sizes. These two magnetic fractions are generally discussed as separate fractions, but we suggest that they could actually be genetically linked.

Sources and proxy potential of long chain alkyl diols in lacustrine environments

Long chain 1,13- and 1,15-alkyl diols form the base of a number of recently proposed proxies used for climate reconstruction. However, the sources of these lipids and environmental controls on their distribution are still poorly constrained. We have analyzed the long chain alkyl diol (LCD) composition of cultures of ten eustigmatophyte species, with three species from different families grown at various temperatures, to identify the effect of species composition and growth temperature on the LCD distribution. The results were compared with the LCD distribution of sixty-two lake surface sediments, and with previously reported LCD distributions from marine environments. The different families within the Eustigmatophyceae show distinct LCD patterns, with the freshwater family Eustigmataceae most closely resembling LCD distributions in both marine and lake environments. Unlike the other two eustigmatophyte families analyzed (Monodopsidaceae and Goniochloridaceae), C28 and C30 1,13-alkyl diols and C30 and C32 1,15-alkyl diols are all relatively abundant in the family Eustigmataceae, while the mono-unsaturated C32 1,15-alkyl diol was below detection limit. In contrast to the marine environment, LCD distributions in lakes did not show a clear relationship with temperature. The Long chain Diol Index (LDI), a proxy previously proposed for sea surface temperature reconstruction, showed a relatively weak correlation (R2 = 0.33) with mean annual air temperature used as an approximation for annual mean surface temperature of the lakes. A much-improved correlation (R2 = 0.74, p-value<0.001) was observed applying a multiple linear regression analysis between LCD distributions and lake temperatures reconstructed using branched tetraether lipid distributions. The obtained regression model provides good estimates of temperatures for cultures of the family Eustigmataceae, suggesting that algae belonging to this family have an important role as a source for LCDs in lacustrine environments, or, alternatively, that the main sources of LCDs are similarly affected by temperature as the Eustigmataceae. The results suggest that LCDs may have the potential to be applicable as a palaeotemperature proxy for lacustrine environments, although further calibration work is still required.

Rare earth element contents and sources in phosphorites from Pacific seamounts

Distribution of rare earth elements (REE) was studied in phosphorites collected from seamounts at depths from about 400 to 3600 m. In general phosphorites are characterized by high REE con¬tent, by a strong negative Ce anomaly, by a slight positive Gd anomaly, and by slight enrichment in heavy REE, which is also characteristic of seawater, where, to certain extent, composition of REE depends on depth. Comparison of REE composition in phosphorites and in seawater from the Northwest Pacific by means of Q-mode factor analysis revealed that REE have been transported into the phosphorites from various water depths following submergence of the seamounts. This corresponds to paleotectonic reconstructions, but is only partially consistent with age determinations of phosphorites.

Combined effects of different CO2 levels and N sources on the diazotrophic cyanobacterium Trichodesmium

To predict effects of climate change and possible feedbacks, it is crucial to understand the mechanisms behind CO2 responses of biogeochemically relevant phytoplankton species. Previous experiments on the abundant N2 fixers Trichodesmium demonstrated strong CO2 responses, which were attributed to an energy reallocation between its carbon (C) and nitrogen (N) acquisition. Pursuing this hypothesis, we manipulated the cellular energy budget by growing Trichodesmium erythraeum IMS101 under different CO2 partial pressure (pCO2) levels (180, 380, 980 and 1400?µatm) and N sources (N2 and NO3-). Subsequently, biomass production and the main energy-generating processes (photosynthesis and respiration) and energy-consuming processes (N2 fixation and C acquisition) were measured. While oxygen fluxes and chlorophyll fluorescence indicated that energy generation and its diurnal cycle was neither affected by pCO2 nor N source, cells differed in production rates and composition. Elevated pCO2 increased N2 fixation and organic C and N contents. The degree of stimulation was higher for nitrogenase activity than for cell contents, indicating a pCO2 effect on the transfer efficiency from N2 to biomass. pCO2-dependent changes in the diurnal cycle of N2 fixation correlated well with C affinities, confirming the interactions between N and C acquisition. Regarding effects of the N source, production rates were enhanced in NO3-grown cells, which we attribute to the higher N retention and lower ATP demand compared with N2 fixation. pCO2 effects on C affinity were less pronounced in NO3- users than N2 fixers. Our study illustrates the necessity to understand energy budgets and fluxes under different environmental conditions for explaining indirect effects of rising pCO2.