Trace elements in the aerosol at Neumayer Station, Antarctica

Atmospheric trace element concentrations were measured from March 1999 through December 2003 at the Air Chemistry Observatory of the German Antarctic station Neumayer by inductively coupled plasma - quadrupol mass spectrometry (ICP-QMS) and ion chromatogra-phy (IC). This continuous five year long record derived from weekly aerosol sampling re-vealed a distinct seasonal summer maximum for elements linked with mineral dust entry (Al, La, Ce, Nd) and a winter maximum for the mostly sea salt derived elements Li, Na, K, Mg, Ca, and Sr. The relative seasonal amplitude was around 1.7 and 1.4 for mineral dust (La) and sea salt aerosol (Na), respectively. On average a significant deviation regarding mean ocean water composition was apparent for Li, Mg, and Sr which could hardly be explained by mir-abilite precipitation on freshly formed sea ice. In addition we observed all over the year a not clarified high variability of element ratios Li/Na, K/Na, Mg/Na, Ca/Na, and Sr/Na. We found an intriguing co-variation of Se concentrations with biogenic sulfur aerosols (methane sul-fonate and non-sea salt sulfate), indicating a dominant marine biogenic source for this element linked with the marine biogenic sulfur source.

Major element and mineral composition of gabbroic xenoliths and megacrysts from Jeju Island, South Korea

Gabbroic xenoliths and diverse megacrysts (e.g., clinopyroxenes, amphiboles and plagioclases), which correspond to the lithology ranging from gabbro-norite to gabbro, occur in the Pleisto-Holocene alkali basalts from Jeju Island, South Korea. The gabbroic xenoliths consist primarily of moderate-K2O plagioclase, Ti-Al-rich clinopyroxene and CaO-rich orthopyroxene; additionally, TiO2-rich amphibole (kaersutite) and Ti-Fe oxides might or might not be present. The plagioclase is the most dominant phase (approx. 60-70 vol.%). The xenoliths and megacrysts provide evidence for the modal metasomatism of the lower continental crust by the mafic magmas during the Pleistocene. The coarse grain size (up to 5 mm), moderate Mg# [=100xMg/(Mg+Fe(total)) atomic ratio] of pyroxenes (70-77) and textural features (e.g., poikilitic) indicate that the gabbroic xenoliths are consistent with a cumulus origin. The clinopyroxenes from these xenoliths are enriched in REE with smooth convex-upward MREE patterns, which are expected for cumulus minerals formed from a melt enriched in incompatible trace elements. The strikingly similar major and trace element variations and the patterns of constituent minerals clearly indicate a genetic link between the gabbroic xenoliths (plus megacrysts) and the host basalt, indicating that the xenoliths belong to the Jeju Pleisto-Holocene magma system. On the basis of the textural features, the mineral equilibria and the major and trace element variations, the xenoliths appear to have crystallized from basaltic melts at the reservoir-roof environment within the lower crust (4-7 kbars) above the present Moho estimates beneath Jeju Island, where the xenoliths represent wall rocks. Following the consolidation of the xenolith lithologies, volatile- and incompatible element-enriched melt/fluid, as metasomatic agents, infiltrated through the grain boundaries and/or cracks and reacted with the preexisting anhydrous phases, which produced the metasomatic amphiboles. This volatile-enriched melt/fluid could have evolved from the initially anhydrous compositions to the volatile-saturated compositions by the active fractional crystallization in the Jeju Pleisto-Holocene magma system. This process was significant in that it was a relatively young event and played an important role in the formation of the hydrous minerals and the metasomatization of the lower continental crust, which is a plume-impacted area along the Asian continental margin. The major and trace element analyses of the mineral phases from the xenoliths were performed to define the principal geochemical characteristics of the crustal lithosphere segment represented by the studied xenoliths.

Chemical, isotope and mineral composition of hydrothermally altered upper oceanic crust drilled at ODP Site 129-801C

ODP Hole 801C penetrates >400 m into 170-Ma oceanic basement formed at a fast-spreading ridge. Most basalts are slightly (10-20%) recrystallized to saponite, calcite, minor celadonite and iron oxyhydroxides, and trace pyrite. Temperatures estimated from oxygen isotope data for secondary minerals are 5-100°C, increasing downward. At the earliest stage, dark celadonitic alteration halos formed along fractures and celadonite, and quartz and chalcedony formed in veins from low-temperature (<100°C) hydrothermal fluids. Iron oxyhydroxides subsequently formed in alteration halos along fractures where seawater circulated, and saponite and pyrite developed in the host rock and in zones of restricted seawater flow under more reducing conditions. Chemical changes include variably elevated K, Rb, Cs, and H2O; local increases in FeT, Ba, Th, and U; and local losses of Mg and Ni. Secondary carbonate veins have 87Sr/86Sr = 0.706337 - 0.707046, and a negative correlation with d18O results from seawater-basalt interaction. Carbonates could have formed at any time since the formation of Site 801 crust. Variable d13C values (-11.2? to 2.9?) reflect the incorporation of oxidized organic carbon from intercalated sediments and changes in the d13C of seawater over time. Compared to other oceanic basements, a major difference at Site 801 is the presence of two hydrothermal silica-iron deposits that formed from low-temperature hydrothermal fluids at the spreading axis. Basalts associated with these horizons are intensely altered (60-100%) to phyllosilicates, calcite, K-feldspar, and titanite; and exhibit large increases in K, Rb, Cs, Ba, H2O, and CO2, and losses of FeT, Mn, Mg, Ca, Na, and Sr. These effects may be common in crust formed at fast-spreading rates, but are not ubiquitous. A second important difference is that the abundance of brown oxidation halos along fractures at Site 801 is an order of magnitude less than at some other sites (2% vs. 20-30%). Relatively smooth basement topography (<100 m) and high sedimentation rate (8 m/Ma) probably restricted the access of oxygenated seawater. Basement lithostratigraphy and early low-temperature hydrothermal alteration and mineral precipitation in fractures at the spreading axis controlled permeability and limited later flow of oxygenated seawater to restricted depth intervals.

Geochemistry, isotopes, trace elements and fluid inclusion geothermometry at DSDP Hole 83-504B

Stockwork-like metal sulfide mineralizations were found at 910-928 m below seafloor (BSF) in the pillow/dike transition zone of Hole 504B. This is the same interval where most physical properties of the 5.9-m.y.-old crust of the Costa Rica Rift change from those characteristic of Layer 2B to those of Layer 2C. The pillow lavas, breccias, and veins of the stockwork-like zone were studied by transmitted and reflected light microscopy, X-ray diffraction, and electron microprobe analysis. Bulk rock oxygen isotopic analyses as well as isolated mineral oxygen and sulfur isotopic analyses and fluid inclusion measurements were carried out. A complex alteration history was reconstructed that includes three generations of fissures, each followed by precipitation of characteristic hydrothermal mineral parageneses: (1) Minor and local deposition of quartz occurred on fissure walls; adjacent wall rocks were silicified, followed by formation of chlorite and minor pyrite I in the veins, whereas albite, sphene, chlorite and chlorite-expandable clay mixtures, actinolite, and pyrite replaced igneous phases in the host rocks. The hydrothermal fluids responsible for this first stage were probably partially reacted seawater, and their temperatures were at least 200-250° C. (2) Fissures filled during the first stage were reopened and new cracks formed. They were filled with quartz, minor chlorite and chlorite-expandable clay mixtures, traces of epidote, common pyrite, sphalerite, chalcopyrite, and minor galena. During the second stage, hydrothermal fluids were relatively evolved metal- and Si-rich solutions whose temperatures ranged from 230 to 340° C. The fluctuating chemical composition and temperature of the solutions produced a complex depositional sequence of sulfides in the veins: chalcopyrite I, ± Fe-rich sphalerite, chalcopyrite II ("disease"), Fe-poor sphalerite, chalcopyrite III, galena, and pyrite II. (3) During the last stage, zeolites and Mg-poor calcite filled up the remaining spaces and newly formed cracks and replaced the host rock plagioclase. Analcite and stilbite were first to form in veins, possibly at temperatures below 200°C; analcite and earlier quartz were replaced by laumontite at 250°C, whereas calcite formation temperature ranged from 135 to 220°C. The last stage hydrothermal fluids were depleted in Mg and enriched in Ca and 18O compared to seawater and contained a mantle carbon component. This complex alteration history paralleling a complex mineral paragenesis can be interpreted as the result of a relatively long-term evolution of a hydrothermal system with superimposed shorter term fluctuations in solution temperature and composition. Hydrothermal activity probably began close to the axis of the Costa Rica Rift with the overall cooling of the system and multiple fracturing stages due to movement of the crust away from the axis and/or cooling of a magmatic heat source.

Description, geochemistry and mineral composition of ODP Site 193-1189 jasperoids, PACMANUS field

Bright red "jasperoids" were recovered at three positions during Leg 193 drilling below Roman Ruins (Site 1189) in the PACMANUS hydrothermal field. These do not represent fossil exhalative oxide deposits equivalent to those associated with sulfide chimneys at the Roman Ruins seafloor. Rather, they constitute an integral, relatively early stage involving oxidized fluids in the development of veins and breccias that characterize the mostly sulfidic stockwork zone intersected below Roman Ruins in Hole 1189B. They formed by growth of quartz in open spaces created by hydrofracturing, the characteristic feature being mostly euhedral cores dusted by tiny hematite flakes. In one occurrence there are also frondlike aggregates and possible earlier cavity linings of hematite, overgrown by quartz, that potentially formed by maturation of ferruginous gels first deposited in the openings. The trace element geochemistry of the jasperoids, apart from minor enrichment in uranium, provides no indication that they represent subsurface conduits for fluids that deposit Fe-Mn-Si at the seafloor, though this remains a possibility for some such deposits.

Sediment geochemistry and water trace metal concentration in Potter Cove

Recent rapid climate warming at the western Antarctic Peninsula (WAP) results in elevated glacial melting, enhanced sedimentary run-off, increased turbidity and impact of ice-scouring in shallow coastal areas. Discharge of mineral suspension from volcanic bedrock ablation and chronic physical disturbance is expected to influence sessile filter feeders such as the Antarctic soft shell clam Laternula elliptica ( King and Broderip, 1832). We investigated effects of sedimentary run-off on the accumulation of trace metals, and together with physical disturbance, the cumulative effect on oxidative stress parameters in younger and older L. elliptica from two stations in Potter Cove (King George Island, Antarctica) which are distinctly impacted by turbidity and ice-scouring. Fe, Mn, Sr, V and Zn concentrations were slightly higher in sediments of the station receiving more sediment run-off, but not enriched in bivalves of this station. The only element that increased in bivalves experimentally exposed to sediment suspension for 28 days was Mn. Concentration of the waste accumulation biomarker lipofuscin in nervous tissue was higher in L. elliptica from the "exposed" compared to the "less exposed" site, whereas protein carbonyl levels in bivalve mantle tissue were higher at the less sediment impacted site. Tissue metal content and lipofuscin in nervous tissue were generally higher in older compared to younger individuals from both field stations. We conclude that elevated sediment ablation does not per se result in higher metal accumulation in L. elliptica. Instead of direct absorbance from sediment particles, metal accumulation in gills seems to indicate uptake of compounds dissolved in the water column, whereas metals in digestive gland appear to originate from enriched planktonic or detritic food. Accumulation of cellular waste products and potentially reactive metals over lifetime presumably alters L. elliptica physiological performance with age and may contribute to higher stress susceptibility in older animals.

Geochemistry, mineral composition and Ar40/Ar39 ages of dolerites from ODP Leg 180 sites

New trace element analyses are presented for Leg 180 dolerites, basalts from the Papuan Ultramafic Belt (PUB), and basement rocks of Woodlark Island. The Leg 180 dolerites are similar to those from Woodlark Island in being derived from an enriched source but differ from the PUB, which came from a source similar to normal mid-ocean ridge basalts. A reliable 40Ar/39Ar age of 54.0 ± 1.0 Ma has been obtained by step heating of a whole-rock sample from Site 1109, and a similar but less reliable age was obtained for a sample from Site 1118. Plagioclase from Site 1109 did not give a meaningful age. This age is broadly similar to ages from the Dabi volcanics of the nearby Cape Vogel and for the PUB.

Geochemistry of primary and secondary mineral phases in ODP Leg 209 sediments

Primary and secondary mineral phases from Holes 1268A (11 samples), 1272A (9 samples), and 1274A (12 samples) were analyzed by electron microprobe in Bonn and Cologne (Germany). Bulk rock powders of these samples were also analyzed geochemically, including major and trace elements (Paulick et al., 2006, doi:10.1016/j.chemgeo.2006.04.011). Ocean Drilling Program (ODP) Leg 209 Holes 1268A, 1272A, and 1274A differ remarkably in alteration intensity and mineralogy, and details regarding their lithologic characteristics are presented in Bach et al. (2004, doi:10.1029/2004GC000744) and Shipboard Scientific Party (2004, doi:10.2973/odp.proc.ir.209.101.2004). Because of the least altered character of peridotite in Hole 1274A, abundant clinopyroxene, orthopyroxene, olivine, and spinel were analyzed at this site. In Hole 1272A, primary silicates are rare and analyses were restricted to some samples that contain traces of olivine and orthopyroxene. Because of the intensity of alteration, Hole 1268A is devoid of primary phases except spinel. Commonly, alteration is pseudomorphic and serpentinization of olivine and orthopyroxene can be distinguished. Accordingly, compositional variations of the alteration minerals with regard to the precursor minerals are one of the issues investigated in this data report.

Noble metals and associated trace elements in sulfides from the active TAG mound, ODP Site 158-957

Primary sulfides from cores of ODP Holes 158-957M, 158-957C, and 158-957H on the active TAG hydrothermal mound (Mid-Atlantic Ridge, 26°08'N) have been studied for concentrations of several chemical elements. Based on 262 microprobe analyses it has been found that the sulfides have extremely heterogeneous distribution of noble metals (Au, Ag, Pt, and Pd) and several associated elements (Hg, Co, and Se). Noble metals are arranged in the following order in terms of decreasing abundance, i.e. concentration level above detection limits (the number of analyses containing a specific element is given in parentheses): Au (65), Ag (46), Pt (21), and Pd (traces). The associated trace elements have the following series: Co (202), Hg (132), and Se (49). The main carriers of "invisible" portion of the noble metals are represented by pyrite (Au, Hg), marcasite and pyrite (Ag, Co), sphalerite and chalcopyrite (Pt, Pd), and chalcopyrite (Se). Noble metal distribution in sulfides reveals a lateral zonality: maximal concentrations and abundance of Au in chalcopyrite (or Pt and Ag in chalcopyrite and pyrite) increase from the periphery (Hole 957H) to the center (holes 957C and 957M) of the hydrothermal mound, while Au distribution in pyrite displays a reversed pattern. Co concentration increases with depth. Vertical zonality in distribution of the elements mentioned above and their response to evolution of ore genesis are under discussion in the paper.

Mineral and chemical compositions of hydrothermal ores and sediments from the Menez Gwen Hydrothermal Field, Mid-Atlantic Ridge

Mineralogy and geochemistry of sulfide-bearing rocks and ores discovered within the Menez Gwen Hydrothermal Field are studied. Samples were taken during Cruise 49 of R/V Akademik Mstislav Keldysh of the p.p. Shirshov Institute of Oceanology. Mineral composition of rocks and ores were studied by traditional methods of optical microscopy, scanning electron microscopy (CAMSCAN), and microprobe analysis (EPMA SX-50). Contents of trace elements were determined by laser ablation inductively coupled plasma - mass spectrometry (LA-ICP-MS). Zn-Cu ore comprises zonal sulfide chimney intergrowths. Numerous Se-rich copper ore fragments occur in volcanomictic layered gritstones and/or barite slabs. Mineral composition, zonality and association of trace elements in ore are typical of black smokers formed at the basalt base near the Azores Triple Junction in the MAR. Obtained results make it possible to reconstruct formation history of the Menez Gwen Hydrothermal Field into the high-temperature (Cu-Se association in ore clasts), medium-temperature (Zn-Cu-As association in ore), and recent (Ba-SiO2 association) stages.

Whole-rock and mineral geochemistry of ODP Hole 176-735B gabbros

We report mineral chemistry, whole-rock major element compositions, and trace element analyses on Hole 735B samples drilled and selected during Leg 176. We discuss these data, together with Leg 176 shipboard data and Leg 118 sample data from the literature, in terms of primary igneous petrogenesis. Despite mineral compositional variation in a given sample, major constituent minerals in Hole 735B gabbroic rocks display good chemical equilibrium as shown by significant correlations among Mg# (= Mg/[Mg + Fe2+]) of olivine, clinopyroxene, and orthopyroxene and An (=Ca/[Ca + Na]) of plagioclase. This indicates that the mineral assemblages olivine + plagioclase in troctolite, plagioclase + clinopyroxene in gabbro, plagioclases + clinopyroxene + olivine in olivine gabbro, and plagioclase + clinopyroxene + olivine + orthopyroxene in gabbronorite, and so on, have all coprecipitated from their respective parental melts. Fe-Ti oxides (ilmenite and titanomagnetite), which are ubiquitous in most of these rocks, are not in chemical equilibrium with olivine, clinopyroxene, and plagioclase, but precipitated later at lower temperatures. Disseminated oxides in some samples may have precipitated from trapped Fe-Ti-rich melts. Oxides that concentrate along shear bands/zones may mark zones of melt coalescence/transport expelled from the cumulate sequence as a result of compaction or filter pressing. Bulk Hole 735B is of cumulate composition. The most primitive olivine, with Fo = 0.842, in Hole 735B suggests that the most primitive melt parental to Hole 735B lithologies must have Mg# 0.637, which is significantly less than Mg# = 0.714 of bulk Hole 735B. This suggests that a significant mass fraction of more evolved products is needed to balance the high Mg# of the bulk hole. Calculations show that 25%-45% of average Eastern Atlantis II Fracture Zone basalt is needed to combine with 55%-75% of bulk Hole 735B rocks to give a melt of Mg# 0.637, parental to the most primitive Hole 735B cumulate. On the other hand, the parental melt with Mg# 0.637 is far too evolved to be in equilibrium with residual mantle olivine of Fo > 0.89. Therefore, a significant mass fraction of more primitive cumulate (e.g., high Mg# dunite and troctolite) is yet to be sampled. This hidden cumulate could well be deep in the lower crust or simply in the mantle section. We favor the latter because of the thickened cold thermal boundary layer atop the mantle beneath slow-spreading ridges, where cooling and crystallization of ascending mantle melts is inevitable. These observations and data interpretation require reconsideration of the popular concept of primary mantle melts and relationships among the extent of mantle melting, melt production, and the composition and thickness of igneous crust.

Biostratigraphy, magnetostratigraphy, granulometry, isotopes and clay mineral composition of ODP Site 188-1165

During Ocean Drilling Program Leg 188 to Prydz Bay, East Antarctica, several of the shipboard scientists formed the High-Resolution Integrated Stratigraphy Committee (HiRISC). The committee was established in order to furnish an integrated data set from the Pliocene portion of Site 1165 as a contribution to the ongoing debate about Pliocene climate and climate evolution in Antarctica. The proxies determined in our various laboratories were the following: magnetostratigraphy and magnetic properties, grain-size distributions (granulometry), near-ultraviolet, visible, and near-infrared spectrophotometry, calcium carbonate content, characteristics of foraminifer, diatom, and radiolarian content, clay mineral composition, and stable isotopes. In addition to the HiRISC samples, other data sets contained in this report are subsets of much larger data sets. We included these subsets in order to provide the reader with a convenient integrated data set of Pliocene-Pleistocene strata from the East Antarctic continental margin. The data are presented in the form of 14 graphs (in addition to the site map). Text and figure captions guide the reader to the original data sets. Some preliminary interpretations are given at the end of the manuscript.