(Table 2) Geochemistry at DSDP Holes 62-464 and 62-465A

Igneous rocks were recovered from three sites on Hess Rise during Deep Sea Drilling Project Leg 62: altered basalt at Site 464, at the northern end of Hess Rise; and altered trachyte from Site 465, and rounded basalt pebbles in upper Albian to middle Miocene sediments from Site 466, both at the southern end of Hess Rise. Major-, minor-, and trace-element data for basalt from Hole 464 are consistent with these rocks being transitional tholeiites that have undergone low-temperature alteration by reaction with sea water. Trachyte from Hole 465A exhibits as many as three generations of plagioclase along with potash feldspar that are flow aligned in groundmasses alterted to smectites and random mixed-layer clays. Textural evidence indicates that these rocks were eruped subaerially. Chemical data show a range of values when plotted on two- and three-component variation diagrams. The observed variations may result in part from differentiation, but they also reflect the high degree of alteration. Several oxides and elements show strong correlation with H2O+: K2O, SiO2, Rb and Lu decrease and MgO increases with increasing H2O+. These trends, except for that of Lu, are consistent with experimentally determined changes in chemistry that accompany alteration. The trend for Lu has not been previously reported; it may result from a more-intense alteration of the HREE-rich mafic minerals than of the LREE-rich feldspars. Despite their alteration, the trachytes compare favorably with alkalic differentiates from oceanic islands. We interpret Hess Rise as a volcanic platform formed by eruption of off-ridge volcanic rocks onto MORB oceanic crust during the Aptian and Albian stages, after the basement had migrated away from the spreading center. By analogy with present oceanic islands, we propose that early tholeiitic basalts were followed by alkalic basalts and their differentiation products (trachytes), producing a volcanic archipelago of islands and seamounts. Subsequent tectonism and subsidence led to the present state of Hess Rise.

Measurements of organic complexation of iron during the CARUSO-EISENEX experiment

The speciation of strongly chelated iron during the 22-day course of an iron enrichment experiment in the Atlantic sector of the Southern Ocean deviates strongly from ambient natural waters. Three iron additions (ferrous sulfate solution) were conducted, resulting in elevated dissolved iron concentrations (Nishioka, J., Takeda, S., de Baar, H.J.W., Croot, P.L., Boye, M., Laan, P., Timmermans, K.R., 2005, Changes in the concentration of iron in different size fractions during an iron enrichment experiment in the open Southern Ocean. Marine Chemistry, doi:10.1016/j.marchem.2004.06.040) and significant Fe(II) levels (Croot, P.L., Laan, P., Nishioka, J., Strass, V., Cisewski, B., Boye, M., Timmermans, K.R., Bellerby, R.G., Goldson, L., Nightingale, P., de Baar, H.J.W., 2005, Spatial and Temporal distribution of Fe(II) and H2O2 during EisenEx, an open ocean mescoscale iron enrichment. Marine Chemistry, doi:10.1016/j.marchem.2004.06.041). Repeated vertical profiles for dissolved (filtrate < 0.2 µm) Fe(III)-binding ligands indicated a production of chelators in the upper water column induced by iron fertilizations. Abiotic processes (chemical reactions) and an inductive biologically mediated mechanism were the likely sources of the dissolved ligands which existed either as inorganic amorphous phases and/or as strong organic chelators. Discrete analysis on ultra-filtered samples (< 200 kDa) suggested that the produced ligands would be principally colloidal in size (> 200 kDa-< 0.2 µm), as opposed to the soluble fraction (< 200 kDa) which dominated prior to the iron infusions. Yet these colloidal ligands would exist in a more transient nature than soluble ligands which may have a longer residence time. The production of dissolved Fe-chelators was generally smaller than the overall increase in dissolved iron in the surface infused mixed layer, leaving a fraction (about 13-40%) of dissolved Fe not bound by these dissolved Fe-chelators. It is suggested that this fraction would be inorganic colloids. The unexpected persistence of such high inorganic colloids concentrations above inorganic Fe-solubility limits illustrates the peculiar features of the chemical iron cycling in these waters. Obviously, the artificial about hundred-fold increase of overall Fe levels by addition of dissolved inorganic Fe(II) ions yields a major disruption of the natural physical-chemical abundances and reactivity of Fe in seawater. Hence the ensuing responses of the plankton ecosystem, while in itself significant, are not necessarily representative for a natural enrichment, for example by dry or wet deposition of aeolian dust. Ultimately, the temporal changes of the Fe(III)-binding ligand and iron concentrations were dominated by the mixing events that occurred during EISENEX, with storms leading to more than an order of magnitude dilution of the dissolved ligands and iron concentrations. This had strongest impact on the colloidal size class (> 200 kDa-< 0.2 µm) where a dramatic decrease of both the colloidal ligand and the colloidal iron levels (Nishioka, J., Takeda, S., de Baar, H.J.W., Croot, P.L., Boye, M., Laan, P., Timmermans, K.R., 2005, Changes in the concentration of iron in different size fractions during an iron enrichment experiment in the open Southern Ocean. Marine Chemistry, doi:10.1016/j.marchem.2004.06.040) was observed.

(Table 1) Bulk and clay mineralogy at DSDP Leg 66 Holes

During Leg 66 eight sites on an active margin transect off southern Mexico were drilled in order to determine the nature of ocean-continent transition across a subduction zone. Present outcrops of Mesozoic to Precambrian basement at the coast intruded by Mesozoic magmas within only 65 km of the Middle America Trench axis indicate truncation of the continental margin, tectonic removal of an accretionary zone, and consumption of ocean sediments and crust by subduction.

Dissolved iron measured along surface transects of the CARUSO-EISENEX experiment

Measurements of Fe(II) and H2O2 were carried out in the Atlantic sector of the Southern Ocean during EisenEx, an iron enrichment experiment. Iron was added on three separate occasions, approximately every 8 days, as a ferrous sulfate (FeSO4) solution. Vertical profiles of Fe(II) showed maxima consistent with the plume of the iron infusion. While H2O2 profiles revealed a corresponding minima showing the effect of oxidation of Fe(II) by H2O2, observations showed detectable Fe(II) concentrations existed for up to 8 days after an iron infusion. H2O2 concentrations increased at the depth of the chlorophyll maximum when iron concentrations returned to pre-infusion concentrations (<80 pM) possibly due to biological production related to iron reductase activity. In this work, Fe(II) and dissolved iron were used as tracers themselves for subsequent iron infusions when no further SF6 was added. EisenEx was subject to periods of weak and strong mixing. Slow mixing after the second infusion allowed significant concentrations of Fe(II) and Fe to exist for several days. During this time, dissolved and total iron in the infusion plume behaved almost conservatively as it was trapped between a relict mixed layer and a new rain-induced mixed layer. Using dissolved iron, a value for the vertical diffusion coefficient Kz=6.7±0.7 cm**2/s was obtained for this 2-day period. During a subsequent surface survey of the iron-enriched patch, elevated levels of Fe(II) were found in surface waters presumably from Fe(II) dissolved in the rainwater that was falling at this time. Model results suggest that the reaction between uncomplexed Fe(III) and O2? was a significant source of Fe(II) during EisenEx and helped to maintain high levels of Fe(II) in the water column. This phenomenon may occur in iron enrichment experiments when two conditions are met: (i) When Fe is added to a system already saturated with regard to organic complexation and (ii) when mixing processes are slow, thereby reducing the dispersion of iron into under-saturated waters.

Net community production, Thorium-234 activity and particle flux during the Southern Ocean iron fertilization experiment LOHAFEX

A closed eddy core in the Subantarctic Atlantic Ocean was fertilized twice with two tons of iron (as FeSO4), and the 300 km**2 fertilized patch was studied for 39 days to test whether fertilization enhances downward particle flux into the deep ocean. Chlorophyll a and primary productivity doubled after fertilization, and photosynthetic quantum yield (FV/FM) increased from 0.33 to >0.40. Silicic acid (<2 µmol/L) limited diatoms, which contributed <10% of phytoplankton biomass. Copepods exerted high grazing pressure. This is the first study of particle flux out of an artificially fertilized bloom with very low diatom biomass. Net community production (NCP) inside the patch, estimated from O2:Ar ratios, averaged 21 mmol POC/m**2/d, probably ±20%. 234Th profiles implied constant export of ~6.3 mmol POC/m**2/d in the patch, similar to unfertilized waters. The difference between NCP and 234Th-derived export partly accumulated in the mixed layer and was partly remineralized between the mixed layer and 100 m. Neutrally buoyant sediment traps at 200 and 450 m inside and outside the patch caught mostly <1.1 mmol POC/m**2/d, predominantly of fecal origin; flux did not increase upon fertilization. Our data thus indicate intense flux attenuation between 100 and 200 m, and probably between the mixed layer and 100 m. We attribute the lack of fertilization-induced export to silicon limitation of diatoms and reprocessing of sinking particles by detritus feeders. Our data are consistent with the view that nitrate-rich but silicate-deficient waters are not poised for enhanced particle export upon iron addition.

Late Paleocene to Eocene stable isotope record od ODP Site 143-865

An expanded and largely complete upper Paleocene to upper Eocene section was recovered from the pelagic cap overlying Allison Guyot, Mid-Pacific Mountains at Ocean Drilling Program (ODP) Site 865 (18°26'N, 179°33'W; paleodepth 1300-1500 m). Reconstructions show that the site was within a few degrees of the equator during the Paleogene. Because no other Paleogene sections have been recovered in the Pacific Ocean at such a low latitude, Site 865 provides a unique record of equatorial Pacific paleoceanography. Detailed stable isotopic investigations were conducted on three planktonic foraminiferal taxa (species of Acarinina, Morozovella, and Subbotina). We studied benthic foraminiferal isotopes at much lower resolution on species of Cibicidoides and Lenticulina, Nuttallides truempyi and Gavelinella beccariiformis, because of their exceptional rarity. The d18O and d13C stratigraphies from Site 865 are generally similar to those derived from other Paleocene and Eocene sections. The planktonic foraminiferal records at Site 865, however, include significantly less short-term, single-sample variability than those from higher-latitude sites, indicating that this tropical, oligotrophic location had a comparatively stable water column structure with a deep mixed layer and less seasonal variability. Low-amplitude (0.1-0.8 per mil) oscillations on timescales of 250,000 to 300,000 years correlate between the d13C records of all planktonic taxa and may represent fluctuations in the mixing intensity of surface waters. Peak sea surface temperatures of 24°-25°C occurred in the earliest Eocene, followed by a rapid cooling of 3-6°C in the late early Eocene. Temperatures remained cool and stable through the middle Eocene. In the late Eocene, surface water temperatures decreased further. Vertical temperature gradients decreased dramatically in the late Paleocene and were relatively constant through much of the Eocene but increased markedly in the late Eocene. Intermediate waters warmed through the late Paleocene, reaching a maximum temperature of 10°C in the early Eocene. Cooling in the middle and late Eocene paralleled that of surface waters, with latest Eocene temperatures below 5°C. Extinction patterns of benthic foraminifera in the latest Paleocene were similar to those observed at other Pacific sites and were coeval with a short-term, very rapid negative excursion in d13C values in planktonic and benthic taxa as at other sites. During this excursion, benthic foraminiferal d18O values decreased markedly, indicating warming of 4 to 6°C for tropical intermediate waters, while planktonic taxa show slight warming (1°C) followed by 2°C of cooling. Convergence of d18O values of planktonic and benthic foraminifera suggests that thermal gradients in the water column in this tropical location collapsed during the excursion. These data are consistent with the hypothesis that equatorial Pacific surface waters were a potential source of warm, higher salinity waters which filled portions of the deep ocean in the latest Paleocene. Oxygen isotopic data indicate that equator to high southern latitude sea surface thermal gradients decreased to as little as 4°C at the peak of the excursion, suggesting some fundamental change in global heat transport.

Alkenones and SST of surface sediments (Appendix)

We have analysed alkenones in 149 surface sediments from the eastern South Atlantic in order to establish a sediment-based calibration of the U37K' paleotemperature index. Our study covers the major tropical to subpolar production systems and sea-surface temperatures (SST's) between 0° and 27°C. In order to define the most suitable calibration for this region, the U37K' values were correlated to seasonal, annual, and production-weighted annual mean atlas temperatures and compared to previously published culture and core-top calibrations. The best linear correlation between U37K' and SST was obtained using annual mean SST from 0 to 10 m water depth (U37K' = 0.033 T + 0.069, r**2 = 0.981). Data scattering increased significantly using temperatures of waters deeper than 20 m, suggesting that U37K' reflects mixed-layer SST and that alkenone production at thermocline depths was not high enough to significantly bias the mixed-layer signal. Regressions based on both production-weighted and on actual annual mean atlas SST were virtually identical, indicating that regional variations in the seasonality of primary production have no discernible effect on the U37K' vs. SST relationship. Comparison with published core-top calibrations from other oceanic regions revealed a high degree of accordance. We, therefore, established a global core-top calibration using U37K' data from 370 sites between 60°S and 60°N in the Atlantic, Indian, and Pacific Oceans and annual mean atlas SST (0-29°C) from 0 m water depth. The resulting relationship (U37K' = 0.033 T + 0.044, r**2 = 958) is identical within error limits to the widely used E. huxleyi calibrations of and attesting their general applicability. The observation that core-top calibrations extending over various biogeographical coccolithophorid zones are strongly linear and in better accordance than culture calibrations suggests that U37K' is less species-dependent than is indicated by culture experiments. The results also suggest that variations in growth rate of algae and nutrient availability do not significantly affect the sedimentary record of U37K' in open ocean environments.

(Table 1) Summary statistics of taxa in samples of ODP Hole 181-1123B

Planktonic foraminifera are used to identify late Pliocene-Quaternary near surface water masses on the northeastern flank of Chatham Rise by comparison with faunas in core-tops east of New Zealand. In an overview study, distance measures, ordinations, and discriminant analysis are applied to 32 faunas from Site 1123B to identify similar faunas among 35 core-tops between 35 and 61°S east of New Zealand. Many Site 1123B faunas in the 2.72 myr interval sampled compare with those in core-tops on the northern side of Chatham Rise from a similar latitude, and are identified as transitional zone assemblages now associated with the subtropical gyre. This result is consistent with studies of late Quaternary planktonic foraminifera from this region and suggests that, typically, the Subtropical Front was locked to Chatham Rise through glacial and interglacial periods, at least back to the late Pliocene. However, a fauna at ca. 1.17 Ma compares with subpolar assemblages in core-tops between 44 and 48°S and identifies cooler surface water. Expectedly, closer sampling may reveal additional periods when southern water moved over the northeastern flank of Chatham Rise. Although the dominance of Globorotalia inflata, a species typical of the southern margin of subtropical gyres, is a principal feature of Site 1123B faunas, in a minority it is replaced as the most abundant species by dextral populations of Neogloboquadrina pachyderma, particularly about the time of the middle Pleistocene transition. Close analogues of these variant transitional assemblages are not present in core-tops about Chatham Rise but sediment trap and coretop data from other regions suggest that they identify high fertility in the mixed layer associated with upwelling or mixing of water masses. The proportion of sinistrally coiled Neogloboquadrina pachyderma rises to ca. 0.6 between ca. 2.45 and 2.57 Ma, soon after the intensification of Northern Hemisphere glaciation. Although the coiling data indicate subantarctic near surface water, the species remains rare. As the faunas retain their transitional zone character, only minor entrainment of subantarctic water may have occurred.

Composition of airborne material from yellow snow fallen in the Russian North

Large amounts of dust responsible for bright colors of atmospheric precipitation in the temperate, subpolar and polar zones of the northern hemisphere have been rarely observed. In the twentieth century and in the beginning of the twenty first century in the Northern European Russia such events were not registered up to March 25-26, 2008. At that time in some parts of the Arkhangel'sk region, Komi Republic, and Nenets Autonomous Area atmospheric precipitation as sleet and rain responsible for sand- and saffron colors of ice crust formation on the snow surface was observed. During detailed mineralogical, geochemical, pollen, diatom and meteorological investigations it was established that semidesert and steppe regions of the Northwest Kazakhstan, Volgograd and Astrakhan' regions, and Kalmykia are the main sources of the yellow dust.

Alkenone data of sediment traps off Cape Blanc, NW Africa

We analysed long-chain alkenones in sinking particles and surface sediments from the filamentous upwelling region off Cape Blanc, NW Africa, to evaluate the transfer of surface water signals into the geological record. Our study is based on time-series sediment trap records from 730 m (1990-1991) to 2195-3562 m depth (1988-1991). Alkenone fluxes showed considerable interannual variations and no consistent seasonality. The average flux of C37 and C38 alkenones to the deep traps was 1.9 µg/m**2/d from March 1988 to October 1990 and sevenfold higher in the subsequent year. Alkenone fluxes to the shallower traps were on average twice as high and showed similar temporal variations. The alkenone unsaturation indices UK'37, UK38Me and UK38Et closely mirrored the seasonal variations in sea-surface temperature (weekly Reynolds SST). Time lags of 10-48 days between the SST and unsaturation maxima suggest particle sinking rates of about 80 and 280 m/d for the periods of low and high alkenone fluxes, respectively. The average flux-weighted UK'37 temperature for the 4-year time series of the deeper traps was 22.1°C, in perfect agreement with the mean weekly SST for the same period. This and the comparison with seasonal temperature variations in the upper 100 m of the water column suggests that UK'37 records principally the yearly average of the mixed-layer temperature in this region. A comparison between the average annual alkenone fluxes to the lower traps (2400 µg/m**2/yr) and into the underlying sediments (4 µg/m**2/yr) suggests that only about 0.2% of the alkenones reaching the deep ocean became preserved in the sediments. The flux-weighted alkenone concentrations also decreased considerably, from 2466 µg/gC in the water column to 62 µg/gC in the surface sediments. Such a low degree of alkenone preservation is typical for slowly accumulating oxygenated sediments. Despite these dramatic diagenetic alkenone losses, the UK'37 ratio was not affected. The average UK'37 value of the sediments (0.796±0.010 or 22.3±0.3°C) was identical within error limits to the 4-year average of the lower traps. The unsaturation indices for C38 alkenones and the ratio between C37 and C38 alkenones also revealed a high degree of stability. Our results do not support the hypothesis that UK'37 is biased towards higher values during oxic diagenesis.