Geochemistry on sediment profile PS69/335

During RV Polarstern cruise ANT-XXIII/4 in 2006, a gravity core (PS69/335-2) and a giant box core (PS69/335-1) were retrieved from Maxwell Bay off King George Island (KGI). Comprehensive geochemical (bulk parameters, quantitative XRF, Inductively Coupled Plasma Mass Spectrometry) and radiometric dating analyses (14C, 210Pb) were performed on both cores. A comparison with geochemical data from local bedrock demonstrates a mostly detrital origin for the sediments, but also points to an overprint from changing bioproductivity in the overlying water column in addition to early diagenetic processes. Furthermore, ten tephra layers that were most probably derived from volcanic activity on Deception Island were identified. Variations in the vertical distribution of selected elements in Maxwell Bay sediments further indicate a shift in source rock provenance as a result of changing glacier extents during the past c. 1750 years that may be linked to the Little Ice Age and the Medieval Warm Period. Whereas no evidence for a significant increase in chemical weathering rates was found, 210Pb data revealed that mass accumulation rates in Maxwell Bay have almost tripled since the 1940s (0.66 g cm-2 yr-1 in AD 2006), which is probably linked to rapid glacier retreat in this region due to recent warming.

Aerosols in the Arctic

In this monograph on the basis of materials obtained by the author and his colleagues in Arctic expeditions of 1991-2005 and of published data results of studies effect of aerosols on environmental conditions and marine sedimentation in the Arctic are summarizes. Processes of aeolian transport and transformation of sedimentary material from sources to places of its accumulation in bottom sediments are described. Results of this study can be used to assess current state of ecosystem of Arctic seas and as a background for evaluation of possible human impact on nature during exploration of mineral resources of the Arctic shelf. For oceanographers, geochemists, geoecologists.

Chemical composition of sediment core GeoB12309-5 from the northern Arabian Sea, its pore water profile and age depth relationship as well as CTD data obtained during cruise M74/3

The Arabian Sea off the Pakistan continental margin is characterized by one of the world's largest oxygen minimum zones (OMZ). The lithology and geochemistry of a 5.3 m long gravity core retrieved from the lower boundary of the modern OMZ (956 m water depth) were used to identify late Holocene changes in oceanographic conditions and the vertical extent of the OMZ. While the lower part of the core (535 - 465 cm, 5.04 - 4.45 cal kyr BP, Unit 3) is strongly bioturbated indicating oxic bottom water conditions, the upper part of the core (284 - 0 cm, 2.87 cal kyr BP to present, Unit 1) shows distinct and well-preserved lamination, suggesting anoxic bottom waters. The transitional interval from 465 to 284 cm (4.45 - 2.87 cal kyr BP, Unit 2) contains relicts of lamination which are in part intensely bioturbated. These fluctuations in bioturbation intensity suggest repetitive changes between anoxic and oxic/suboxic bottom-water conditions between 4.45 - 2.87 cal kyr BP. Barium excess (Baex) and total organic carbon (TOC) contents do not explain whether the increased TOC contents found in Unit 1 are the result of better preservation due to low BWO concentrations or if the decreased BWO concentration is a result of increased productivity. Changes in salinity and temperature of the outflowing water from the Red Sea during the Holocene influenced the water column stratification and probably affected the depth of the lower boundary of the OMZ in the northern Arabian Sea. Even if we cannot prove certain scenarios, we propose that the observed downward shift of the lower boundary of the OMZ was also impacted by a weakened Somali Current and a reduced transport of oxygen-rich Indian Central Water into the Arabian Sea, both as a response to decreased summer insolation and the continuous southward shift of the Intertropical Convergence Zone during the late Holocene.

Geochemistry, lithology, and bulk density of Cricket Flat paleosol samples

The high-resolution marine isotope climate record indicates pronounced global cooling during the Langhian (16-13.8 Ma), beginning with the warm middle Miocene climatic optimum and ending with significant Antarctic ice sheet expansion and the transition to "icehouse" conditions. Terrestrial paleoclimate data from this interval is sparse and sometimes conflicting. In particular, there are gaps in the terrestrial record in the Pacific Northwest during the late Langhian and early Serravallian between about 14.5 and 12.5 Ma. New terrestrial paleoclimate data from this time and region could reconcile these conflicting records. Paleosols are particularly useful for reconstructing paleoenvironment because the rate and style of pedogenesis is primarily a function of surface environmental conditions; however, complete and well-preserved paleosols are uncommon. Most soils form in erosive environments that are not preserved, or in environments such as floodplains that accumulate in small increments; the resulting cumulic soils are usually thin, weakly developed, and subject to diagenetic overprinting from subsequent soils. The paleosol at Cricket Flat in northeastern Oregon is an unusually complete and well-preserved paleosol from a middle Miocene volcanic sequence in the Powder River Volcanic Field. An olivine basalt flow buried the paleosol at approximately 13.8 ± 0.6 Ma, based on three 40Ar/39Ar dates on the basalt. We described the Cricket Flat paleosol and used its physical and chemical profile and micromorphology to assess pedogenesis. The Cricket Flat paleosol is an Ultisol-like paleosol, chemically consistent with a high degree of weathering. Temperature and rainfall proxies suggest that Cricket Flat received 1120 ± 180 mm precipitation y-1 and experienced a mean annual temperature of 14.5 ± 2.1 °C during the formation of the paleosol, significantly warmer and wetter than today. This suggests slower cooling after the middle Miocene climatic optimum than is seen in the existing paleosol record.

Element and isotope composition of selected volcanics from the Bicol arc, Philippines

Pliocene to recent volcanic rocks from the Bulusan volcanic complex in the southern part of the Bicol arc (Philippines) exhibit a wide compositional range (medium- to high-K basaltic-andesites, andesites and a dacite/rhyolite suite), but are characterised by large ion lithophile element enrichments and HFS element depletions typical of subduction-related rocks. Field, petrographic and geochemical data indicate that the more silicic syn- and post-caldera magmas have been influenced by intracrustal processes such as magma mixing and fractional crystallisation. However, the available data indicate that the Bicol rocks as a group exhibit relatively lower and less variable 87Sr/86Sr ratios (0.7036-0.7039) compared with many of the other subduction-related volcanics from the Philippine archipelago. The Pb isotope ratios of the Bicol volcanics appear to be unlike those of other Philippine arc segments. They typically plot within and below the data field for the Philippine Sea Basin on 207Pb/204Pb versus 206Pb/204Pb and 208Pb/204Pb versus 206Pb/204Pb diagrams, implying a pre-subduction mantle wedge similar to that sampled by the Palau Kyushu Ridge, east of the Philippine Trench. 143Nd/144Nd ratios are moderately variable (0.51285-0.51300). Low silica (<55 wt%) samples that have lower 143Nd/144Nd tend to have high Th/Nd, high Th/Nb, and moderately low Ce/Ce* ratios. Unlike some other arc segments in the Philippines (e.g. the Babuyan-Taiwan segment), there is little evidence for the involvement of subducted terrigenous sediment. Instead, the moderately low 143Nd/144Nd ratios in some of the Bicol volcanics may result from subduction of pelagic sediment (low Ce/Ce*, high Th/Nd, and high Th/Nb) and its incorporation into the mantle wedge via a slabderived partial melt.

Geochemical composition and ages of sediment core BELQ300 obtained from Lake Belau, north Germany

Geochemical and palynological data from an annually laminated core sequence (Lake Belau, Schleswig-Holstein) are interpreted with respect to vegetation and settlement history on the basis of a chronostratigraphical model and archaeological evidence. Most settlement periods indicated by pollen and archaeological data can be geochemically identified in the sediment sequence using tracer elements such as K, Rb, Zr and the K/Zr ratio. Whilst air-borne pollen carry a more regional signal, the sedimentary flux of these trace elements is determined by the allogenic input from the catchment area of the lake and, therefore, provides information about the local history of settlement and agricultural land use in the lake's vicinity. This is exemplified for the period of the middle Neolithic Funnel Beaker Culture ('Iversen landnam'), where a time offset of 250 years between both signals has been detected. In contrast, both geochemical and pollen signals are highly synchronous during the Early Migration Period and the High Medieval Period. Additionally, the Fe/Ca and/or U/Fe ratio may serve as a sensitive tracer for human impact on the trophic state of the lake. The suggested impact of the Romans and the High Medieval civilization can clearly be seen (and quantified) from elevated lead input into Lake Belau sediments at this time. Effects of secular climatic changes on the sedimentary chemistry have not been detected and, if present, seem to have been obliterated by anthropogenic activity.

Utility of thallium and geochemical analysis of Mariana arc sediments from ODP Hole 129-801A and 129-801B

We provide the first exploration of thallium (Tl) abundances and stable isotope compositions as potential tracers during arc lava genesis. We present a case study of lavas from the Central Island Province (CIP) of the Mariana arc, supplemented by representative sedimentary and altered oceanic crust (AOC) inputs from ODP Leg 129 Hole 801 outboard of the Mariana trench. Given the large Tl concentration contrast between the mantle and subduction inputs coupled with previously published distinctive Tl isotope signatures of sediment and AOC, the Tl isotope system has great potential to distinguish different inputs to arc lavas. Furthermore, CIP lavas have well-established inter island variability, providing excellent context for the examination of Tl as a new stable isotope tracer. In contrast to previous work (Nielsen et al., 2006b), we do not observe Tl enrichment or light epsilon 205Tl (where epsilon 205Tl is the deviation in parts per 10,000 of a sample 205Tl/203Tl ratio compared to NIST SRM 997 Tl standard) in the Jurassic-aged altered mafic ocean crust subducting outboard of the Marianas (epsilon 205Tl = - 4.4 to 0). The lack of a distinctive epsilon 205Tl signature may be related to secular changes in ocean chemistry. Sediments representative of the major lithologies from ODP Hole Leg 129 801 have 1-2 orders of magnitude of Tl enrichment compared to the CIP lavas, but do not record heavy signatures (epsilon 205Tl = - 3.0 to + 0.4), as previously found in similar sediment types (epsilon 205Tl > + 2.5; Rehkämper et al., 2004). We find a restricted range of epsilon 205Tl = - 1.8 to - 0.4 in CIP lavas, which overlaps with MORB. One lava from Guguan falls outside this range with epsilon 205Tl = + 1.2. Coupled Cs, Tl and Pb systematics of Guguan lavas suggests that this heavy Tl isotope composition may be due to preferential degassing of isotopically light Tl. In general, the low Tl concentrations and limited isotopic range in the CIP lavas is likely due to the unexpectedly narrow range of epsilon 205Tl found in Mariana subduction inputs, coupled with volcaniclastic, rather than pelagic sediment as the dominant source of Tl. Much work remains to better understand the controls on Tl processing through a subduction zone. For example, Tl could be retained in residual phengite, offering the potential exploration of Cs/Tl ratios as a slab thermometer. However, data for Tl partitioning in phengite (and other micas) is required before developing this application further. Establishing a database of Tl concentrations and stable isotopes in subduction zone lavas with different thermal parameters and sedimentary inputs is required for the future use of Tl as a subduction zone tracer.

Ages of rocks and minerals from the Okhotsk-Chukotka volcanic belt

Current geochronological data on the Okhotsk-Chukotka volcanic belt (OCVB) and relevant problems are discussed. The belt evolution is suggested to be modeled based on 40Ar/39Ar and U-Pb dates more useful in several aspects than common K-Ar or Rb-Sr dates and methods of paleobotanical correlation. Based on new40Ar/39Ar and U-Pb dates obtained for volcanic rocks in the OCVB northern part, the younger (Coniacian) age is established for lower stratigraphic units in the Central Chukotka segment of the belt, and eastward migration of volcanic activity is shown for terminal stages of this structure evolution.

Mineralogy and geochemistry of altered ash, pelagic clay, and a clay vein in basalt from DSDP Leg 62 Holes

Volcanic ash was recovered from lower Aptian to Albian deposits from DSDP Sites 463, 465, and 466; pelagic clay of the upper Pleistocene to Upper Cretaceous was recovered mainly from Site 464, with minor amounts at Sites 465 and 466. We present X-ray-mineralogy data on pelagic clay and altered volcanic ash recovered from the four Leg 62 sites. In addition, two ash samples from Sites 463 and 465, a pelagic clay from Site 464, and a clay vein from the basaltic basement at Site 464 each were analyzed for major, minor, and trace elements. Our purpose is to describe the mineralogy and chemistry of altered ash and pelagic clays, to determine the sources of their parent material, and to delineate the diagenetic history of these clay-rich deposits. Correlation of chemistry and mineralogy of ash and pelagic clay with volcanic rocks suspected to be their parent material is not always straightforward, because weathering and diagenetic alteration caused depletion or enrichment of many elements.

Description, geochemistry, mineralogy and isotopes of sulfides from ODP Site 193-1189, PACMANUS field

Chemical and isotopic data for rare massive and semimassive sulfide samples cored at Site 1189 (Roman Ruins, PACMANUS) suggest their genetic relationship with sulfide chimneys at the seafloor. Sand collected from the hammer drill after commencement of Hole 1189B indicates that at least the lower section of the cased interval was occupied by material similar to the stockwork zone cored from 31 to ~100 meters below seafloor (mbsf) in this hole, but with increased content of barite, sphalerite, and lead-bearing minerals. Fractional crystallization of ascending hydrothermal fluid involving early precipitation of pyrite may explain vertical mineralogical and chemical zoning within the stockwork conduit and the high base and precious metal contents of Roman Ruins chimneys. A mineralized volcaniclastic unit cored deep in Hole 1189A possibly represents the lateral fringe of the conduit system. Lead isotope ratios in the sulfides differ slightly but significantly from those of fresh lavas from Pual Ridge, implying that at least some of the Pb within the Roman Ruins hydrothermal system derived from a deeper, more radiogenic source than the enclosing altered volcanic rocks.

Chemical composition of ferromanganese concretions and host bottom sediments from the Black Sea

Ferromanganese concretions spread out on the bottom of the shallow northwest part of the Black Sea are mainly represented by Fe and Mn nodules on shells and substituted worm tubes. Element composition of these formations was measured by methods of chemical, atomic absorbtion, neutron activation, and ICP-MS analyses. It was established that Fe and Mn contents and Mn/Fe ratio in the concretions varied considerably and which controlled occurrence of several associated metals and minor elements; some of them have not been studied in Black Sea concretions before.

Chemical and isotopic compositions of basaltic glasses and crusts from the Mid-Atlantic Ridge rift valley

Data presented in the paper suggest significant differences between thermodynamic conditions, under which magmatic complexes were formed in MAR at 29°-34°N and 12°-18°N. Melts occurring at 29°-34°N were derived by melting of a mantle source with homogeneous distribution of volatile components and arrived at the surface without significant fractionation, likely, due to their rapid ascent. The MAR segments between 12° and 18°N combine contrasting geodynamic environments of magmatism, which predetermined development of a large plume region with widespread mixing of melting products of geochemically distinct mantle sources. At the same time, this region is characterized by conditions favorable for origin of localized zones of anomalous plume magmatism. These sporadic magmatic sources were spatially restricted to MAR fragments with the Hess crust, whose compositional and mechanical properties were, perhaps, favorable for focusing and localization of plume magmatism. The plume source between 12° and 18°N beneath MAR may be geochemically heterogeneous.

Platinum-group, major, and trace element abundances in ODP Leg 183 basalts

Seventeen basalts from Ocean Drilling Program (ODP) Leg 183 to the Kerguelen Plateau (KP) were analyzed for the platinum-group elements (PGEs: Ir, Ru, Rh, Pt, and Pd), and 15 were analyzed for trace elements. Relative concentrations of the PGEs ranged from ~0.1 (Ir, Ru) to ~5 (Pt) times primitive mantle. These relatively high PGE abundances and fractionated patterns are not accounted for by the presence of sulfide minerals; there are only trace sulfides present in thin-section. Sulfur saturation models applied to the KP basalts suggest that the parental magmas may have never reached sulfide saturation, despite large degrees of partial melting (~30%) and fractional crystallization (~45%). First order approximations of the fractionation required to produce the KP basalts from an ~30% partial melt of a spinel peridotite were determined using the PELE program. The model was adapted to better fit the physical and chemical observations from the KP basalts, and requires an initial crystal fractionation stage of at least 30% olivine plus Cr-spinel (49:1), followed by magma replenishment and fractional crystallization (RFC) that included clinopyroxene, plagioclase, and titanomagnetite (15:9:1). The low Pd values ([Pd/Pt]_pm < 1.7) for these samples are not predicted by currently available Kd values. These Pd values are lowest in samples with relatively higher degrees of alteration as indicated by petrographic observations. Positive anomalies are a function of the behavior of the PGEs; they can be reproduced by Cr-spinel, and titanomagnetite crystallization, followed by titanomagnetite resorption during the final stages of crystallization. Our modeling shows that it is difficult to reproduce the PGE abundances by either depleted upper or even primitive mantle sources. Crustal contamination, while indicated at certain sites by the isotopic compositions of the basalts, appears to have had a minimal affect on the PGEs. The PGE abundances measured in the Kerguelen Plateau basalts are best modeled by melting a primitive mantle source to which was added up to 1% of outer core material, followed by fractional crystallization of the melt produced. This reproduces both the abundances and patterns of the PGEs in the Kerguelen Plateau basalts. An alternative model for outer core PGE abundances requires only 0.3% of outer core material to be mixed into the primitive mantle source. While our results are clearly model dependent, they indicate that an outer core component may be present in the Kerguelen plume source.

PM2.5, PM10, and PM10-associated elements in the air in Bamako, Mali (2012-2013)

Saharan dust incursions and particulates emitted from human activities degrade air quality throughout West Africa, especially in the rapidly expanding urban centers in the region. Particulate matter (PM) that can be inhaled is strongly associated with increased incidence of and mortality from cardiovascular and respiratory diseases and cancer. Air samples collected in the capital of a Saharan-Sahelian country (Bamako, Mali) between September 2012 - July 2013 were found to contain inhalable PM concentrations that exceeded World Health Organization (WHO) and US Environmental Protection Agency (USEPA) PM2.5 and PM10 24-h limits 58 - 98% of days and European Union (EU) PM10 24-h limit 98% of days. Mean concentrations were 1.2-to-4.5 fold greater than existing limits. Inhalable PM was enriched in transition metals, known to produce reactive oxygen species and initiate the inflammatory reaction, and other potentially bioactive and biotoxic metals/metalloids. Eroded mineral dust composed the bulk of inhalable PM, whereas most enriched metals/metalloids were likely emitted from oil combustion, biomass burning, refuse incineration, vehicle traffic, and mining activities. Human exposure to inhalable PM and associated metals/metalloids over 24-h was estimated. The findings indicate that inhalable PM in the Sahara-Sahel region may present a threat to human health, especially in urban areas with greater inhalable PM and transition metal exposure.