(Table, Appendix C) Metal content of nodules at Sea Scope stations based upon XRF analyses at the Ore Microscopy Laboratory, Washington State Unicersity, USA

New information on possible resource value of sea floor manganese nodule deposits in the eastern north Pacific has been obtained by a study of records and collections of the 1972 Sea Scope Expedition. Nodule abundance (percent of sea floor covered) varies greatly, according to photographs from eight stations and data from other sources. All estimates considered reliable are plotted on a map of the region. Similar maps show the average content of Ni, Cu, Mn and Co at 89 stations from which three or more nodules were analyzed. Variations in nodule metal content at each station are shown graphically in an appendix, where data on nodule sizes are also given. Results of new analyses of 420 nodules from 93 stations for mn, fe, ni, cu, CO, and zn are listed in another appendix. Relatively high Ni + Cu content is restricted chiefly to four groups of stations in the equatorial region, where group averages are 1.86, 1.99, 2.47, and 2.55 weight-percent. Prepared for United States Department of the Interior, Bureau of Mines. Grant no. GO284008-02-MAS. - NTIS PB82-142571.

Biomarker in Heinrich event layers

There are controversies regarding the origin of Heinrich layer 3 (H3), the massive ice-rafting and meltwater event in the North Atlantic during the last glacial cycle spanning a time window between 29 and 30 kyr B.P. Some argue in favor of a Laurentide Ice Sheet source similar to other Heinrich layers, while a contending view argues for the European ice sheet source. Existing geochemical proxies such as 40Ar/39Ar, 206Pb/204Pb, or epsilon-Nd, etc., could not be used to distinguish among various sources of ice-rafted debris in H3 because of their low abundances, suggesting a background glacial sediment signal. In order to circumvent this problem a biomarker-based approach is used to characterize the provenance of H layers 2, 3, and 4 and other non-Heinrich layers. The presence of hopanes and steranes and their aromatic counterparts in the H layers is incompatible with Recent sediments and is attributed to the transportation of organic matter because of the glacial erosion of source rocks. The most diagnostic and useful signatures of this ancient organic matter in the H layers are the dominance of C34 hopanoids over C33 and the occurrence of isorenieratane along with palaerenieratane. Biomarkers signatures in H layers 2 and 3 of the Labrador Sea suggest no difference in their source. Hydrocarbon distributions suggest that these sediments were derived from the Middle to Late Ordovician and Silurian source rocks of the Hudson Bay of eastern Canada. Biomarker data of the H layer 4 from the northwest Atlantic reveal that the sediments of this layer have a similar source to the H layers in the Labrador Sea.

Terrigenous input and marine productivity for the Pacific sector of the Southern Ocean based on lipid biomarkers

In this study, we present a new multiproxy data set of terrigenous input, marine productivity and sea surface temperature (SST) from 52 surface sediment samples collected along E-W transects in the Pacific sector of the Southern Ocean. Allochtonous terrigenous input was characterized by the distribution of plant wax n-alkanes and soil-derived branched glycerol dialkyl glycerol tetraethers (brGDGTs). 230Th-normalized burial rates of both compound groups were highest close to the potential sources in Australia and New Zealand and are strongly related to lithogenic contents, indicating common sources and transport. Detection of both long-chain n-alkanes and brGDGTs at the most remote sites in the open ocean strongly suggests a primarily eolian transport mechanism to at least 110°W, i.e. by prevailing westerly winds. Two independent organic SST proxies were used, the UK'37 based on long-chain alkenones, and the TEX86 based on isoprenoid GDGTs. Both, UK'37 and TEX86 indices show robust relationships with temperature over a temperature range between 0.5 and 20°C, likely implying different seasonal and regional imprints on the temperature signal. While alkenone-based temperature estimates reliably reflect modern SST even at the low temperature end, large temperature residuals are observed for the polar ocean using the TEX86 index. 230Th-normalized burial rates of alkenones are highest close to the Subtropical Front and are positively related to lithogenic fluxes throughout the study area. In contrast, highest isoGDGT burial south of the Antarctic Polar Front is not related with dust flux but may be largely controlled by diatom blooms, and thus high opal fluxes during austral summer.

Reconstructions of eolian dust accumulation in northwest African margin sediments

Reconstructions of eolian dust accumulation in northwest African margin sediments provide important continuous records of past changes in atmospheric circulation and aridity in the region. Existing records indicate dramatic changes in North African dust emissions over the last 20 ka, but the limited spatial extent of these records and the lack of high-resolution flux data do not allow us to determine whether changes in dust deposition occurred with similar timing, magnitude and abruptness throughout northwest Africa. Here we present new records from a meridional transect of cores stretching from 31°N to 19°N along the northwest African margin. By combining grain size endmember modeling with 230Th-normalized fluxes for the first time, we are able to document spatial and temporal changes in dust deposition under the North African dust plume throughout the last 20 ka. Our results provide quantitative estimates of the magnitude of dust flux changes associated with Heinrich Stadial 1, the Younger Dryas, and the African Humid Period (AHP; ~11.7-5 ka), offering robust targets for model-based estimates of the climatic and biogeochemical impacts of past changes in North African dust emissions. Our data suggest that dust fluxes between 8 and 6 ka were a factor of ~5 lower than average fluxes during the last 2 ka. Using a simple model to estimate the effects of bioturbation on dust input signals, we find that our data are consistent with abrupt, synchronous changes in dust fluxes in all cores at the beginning and end of the AHP. The mean ages of these transitions are 11.8±0.2 ka (1Sigma) and 4.9±0.2 ka, respectively.

Nitrite consumption and associated isotope changes during a river flood event in the Elbe river

In oceans, estuaries, and rivers, nitrification is an important nitrate source, and stable isotopes of nitrate are often used to investigate recycling processes (e.g. remineralisation, nitrification) in the water column. Nitrification is a two-step process, where ammonia is oxidised via nitrite to nitrate. Nitrite usually does not accumulate in natural environments, which makes it difficult to study the single isotope effect of ammonia oxidation or nitrite oxidation in natural systems. However, during an exceptional flood in the Elbe River in June 2013, we found a unique co-occurrence of ammonium, nitrite, and nitrate in the water column, returning towards normal summer conditions within 1 week. Over the course of the flood, we analysed the evolution of d15N-[NH4]+ and d15N-[NO2]- in the Elbe River. In concert with changes in suspended particulate matter (SPM) and d15N SPM, as well as nitrate concentration, d15N-NO3 - and d18O-[NO3] -, we calculated apparent isotope effects during net nitrite and nitrate consumption. During the flood event, > 97 % of total reactive nitrogen was nitrate, which was leached from the catchment area and appeared to be subject to assimilation. Ammonium and nitrite concentrations increased to 3.4 and 4.4 µmol/l, respectively, likely due to remineralisation, nitrification, and denitrification in the water column. d15N-[NH4]+ values increased up to 12 per mil, and d15N-[NO2]- ranged from -8.0 to -14.2 per mil. Based on this, we calculated an apparent isotope effect 15-epsilon of -10.0 ± 0.1 per mil during net nitrite consumption, as well as an isotope effect 15-epsilon of -4.0 ± 0.1 per mil and 18-epsilon of -5.3 ± 0.1 per mil during net nitrate consumption. On the basis of the observed nitrite isotope changes, we evaluated different nitrite uptake processes in a simple box model. We found that a regime of combined riparian denitrification and 22 to 36 % nitrification fits best with measured data for the nitrite concentration decrease and isotope increase.

Argon, uranium, thorium and lead composition and ages of ODP Leg 180 sites

During Ocean Drilling Program (ODP) Leg 180, 11 sites were drilled in the vicinity of the Moresby Seamount to study processes associated with the transition from continental rifting to seafloor spreading in the Woodlark Basin. This paper presents thermochronologic (40Ar/39Ar, 238U/206Pb, and fission track) results from igneous rocks recovered during ODP Leg 180 that help constrain the latest Cretaceous to present-day tectonic development of the Woodlark Basin. Igneous rocks recovered (primarily from Sites 1109, 1114, 1117, and 1118) consist of predominantly diabase and metadiabase, with minor basalt and gabbro. Zircon ion microprobe analyses gave a 238U/206Pb age of 66.4 ± 1.5 Ma, interpreted to date crystallization of the diabase. 40Ar/39Ar plagioclase apparent ages vary considerably according to the degree to which the diabase was altered subsequent to crystallization. The least altered sample (from Site 1109) yielded a plagioclase isochron age of 58.9 ± 5.8 Ma, interpreted to represent cooling following intrusion. The most altered sample (from Site 1117) yielded an isochron age of 31.0 ± 0.9 Ma, interpreted to represent a maximum age for the timing of subsequent hydrothermal alteration. The diabase has not been thermally affected by Miocene-Pliocene rift-related events, supporting our inference that these rocks have remained at shallow and cool levels in the crust (i.e., upper plate) since they were partially reset as a result of middle Oligocene hydrothermal alteration. These results suggest that crustal extension in the vicinity of the Moresby Seamount, immediately west of the active seafloor spreading tip, is being accommodated by normal faulting within latest Cretaceous to early Paleocene oceanic crust. Felsic clasts provide additional evidence for middle Miocene and Pliocene magmatic events in the region. Two rhyolitic clasts (from Sites 1110 and 1111) gave zircon 238U/206Pb ages of 15.7 ± 0.4 Ma and provide evidence for Miocene volcanism in the region. 40Ar/39Ar total fusion ages on single grains of K-feldspar from these clasts yielded younger apparent ages of 12.5 ± 0.2 and 14.4 ± 0.6 Ma due to variable sericitization of K-feldspar phenocrysts. 238U/206Pb zircon, 40Ar/39Ar K-feldspar and biotite total fusion, and apatite fission track analysis of a microgranite clast (from Site 1108) provide evidence for the existence of a rapidly cooled 3.0 to 1.8 Ma granitic protolith. The clast may have been transported longitudinally from the west (e.g., from the D'Entrecasteaux Islands). Alternatively, it may have been derived from a more proximal, but presently unknown, source in the vicinity of the Moresby Seamount.

(Table 1) Strontium concentration and isotope ratios of carbonates from DSDP Holes 69-504B as well as 83-504B and fish debris samples from Indian and Pacific Ocean sediments

Recent revisions of the geological time scale by Kent and Gradstein (in press) suggest that, on the average, Cretaceous magnetic anomalies are approximately 10 m.y. older than in Larson and Hilde's (1975) previous time scale. These revised basement ages change estimates for the duration of alteration in the ocean crust, based on the difference between secondary-mineral isochron ages and magnetic isochron-crustal ages, from 3 to approximately 13 m.y. In addition to the revised time scale, Burke et al.'s (1982) new data on the temporal variation of 87Sr/86Sr in seawater allow a better understanding of the timing of alteration and more realistic determinations of water/rock ratios during seawater-basalt interaction. Carbonates from all DSDP sites which reached Layer 2 of Atlantic crust (Sites 105, 332, 417, and 418) are deposited within 10-15 m.y. of crustal formation from solutions with 87Sr/86Sr ratios identical to unaltered or contemporaneous seawater. Comparisons of the revised seawater curve with the 87Sr/86Sr of basement carbonates is consistent with a duration of approximately 10-15 m.y. for alteration in the ocean crust. Our preliminary Sr and 87Sr/86Sr data for carbonates from Hole 504B, on 5.9-m.y.-old crust south of the Costa Rica Rift, suggest that hydrous solutions from which carbonates precipitated contained substantial amounts of basaltic Sr. For this reason, carbonate 87Sr/86Sr cannot be used to estimate the duration of alteration at this site. A basalt-dominated alteration environment at Hole 504B is consistent with heat-flow evidence which indicates rapid sediment burial of crust at the Costa Rica Rift, sealing it from access by seawater and resulting in unusually low water/rock ratios during alteration.