Aircraft and satellite derived arctic BrO profiles of the tropospheric column

We derive tropospheric column BrO during the ARCTAS and ARCPAC field campaigns in spring 2008 using retrievals of total column BrO from the satellite UV nadir sensors OMI and GOME-2 using a radiative transfer model and stratospheric column BrO from a photochemical simulation. We conduct a comprehensive comparison of satellite-derived tropospheric BrO column to aircraft in-situ observations of BrO and related species. The aircraft profiles reveal that tropospheric BrO, when present during April 2008, was distributed over a broad range of altitudes rather than being confined to the planetary boundary layer (PBL). Perturbations to the total column resulting from tropospheric BrO are the same magnitude as perturbations due to longitudinal variations in the stratospheric component, so proper accounting of the stratospheric signal is essential for accurate determination of satellite-derived tropospheric BrO. We find reasonably good agreement between satellite-derived tropospheric BrO and columns found using aircraft in-situ BrO profiles, particularly when satellite radiances were obtained over bright surfaces (albedo >0.7), for solar zenith angle <80° and clear sky conditions. The rapid activation of BrO due to surface processes (the bromine explosion) is apparent in both the OMI and GOME-2 based tropospheric columns. The wide orbital swath of OMI allows examination of the evolution of tropospheric BrO on about hourly time intervals near the pole. Low surface pressure, strong wind, and high PBL height are associated with an observed BrO activation event, supporting the notion of bromine activation by high winds over snow.

Concentrations of heavy and precious metals in animals from hydrothermal vents of the Axial Seamount (Juan de Fuca Ridge) and Guaymas Basin (Gulf of California)

A series of samples of inhabitants of hydrothermal vents were collected during the 12-th cruise of R/V Akademik Mstislav Keldysh in Guaymas Basin (the Gulf of California) and the Axial Seamount area (Juan de Fuca Ridge). Concentrations of trace and heavy metals in the tissues of Ridgeia piscesae, Riftia pachyptila, and Paralvinella palmiformis were analyzed. Neutron-activation analysis revealed significantly higher concentrations of uranium in tissues of Paralvinella palmiformis as compared to ambient seawater. Possible reasons for such phenomenon are discussed. The data obtained by neutron-activation method are compared with those obtained by atomic-absorption method for the same tissues analyzed.

Chemical profiles in sediment and basalt at DSDP Hole 74-525A

Forty sediment and four basement basalt samples from DSDP Hole 525A, Leg 74, as well as nine basalt samples from southern and offshore Brazil, were subjected to instrumental neutron activation analysis. Thirty-two major, minor, and trace elements were determined. The downcore element concentration profiles and regression analyses show that the rare earth elements (REE) are present in significant amounts in both the carbonate and noncarbonate phases in sediments; Sr is concentrated in the carbonate phase, and most of the other elements determined exist mainly in the noncarbonate phase. The calculated partition coefficients of the REE between the carbonate phase and the free ion concentrations in seawater are high and increase with decreasing REE ionic radii from 3.9 x 10**6 for La to 15 x 10**6 for Lu. Calculations show that the lanthanide concentrations in South Atlantic seawater have not been changed significantly over the past 70 Ma. The Ce anomaly observed in the carbonate phase is a redox indicator of ancient seawater. Study of the Ce anomaly reveals that seawater was anoxic over the Walvis Ridge during the late Campanian. As the gap between South America and West Africa widened and the Walvis Ridge subsided from late Campanian to late Paleocene times, the water circulation of the South Atlantic improved and achieved oxidation conditions about 54 Ma that are similar to present seawater redox conditions in the world oceans. The chemical compositions of the basement rocks correspond to alkalic basalts, not mid-ocean ridge basalts (MORBs). The results add more evidence to support the hypothesis that the Walvis Ridge was formed by a series of volcanos moving over a "hot spot" near the Mid-Atlantic Ridge. From the chemical composition and REE pattern, one 112 Ma old basalt on the Brazilian continental shelf has been identified as an early stage MORB. To date, this is the oldest oceanic tholeiite recovered from the South Atlantic. This direct evidence indicates that the continental split between South America and Africa commenced > 112 Ma.

Natural oxides, elements and remanent magnetization intensities and directions at DSDP Hole 93-603B

Dark green spherules occur in the lower part of a turbidite in Section 603B-22-3, at the 70 cm level. In all probability these spherules originally consisted of massive glass, but now appear to have become completely altered into smectite. The presence of numerous microscopic fissures in the spherules probably mediated in the alteration process. Judging by the presence of similar spherules at the Cretaceous/Tertiary (K/T) boundary in DSDP Hole 390B, the green spherules are thought to represent diagenetically altered impact ejecta from one large or several smaller extraterrestrial objects at the end of the Cretaceous. The presence of anomalously high concentrations of Ni, Co, and As higher up in the turbidite are in agreement with an expected enrichment of these elements in the K/T boundary clay. However, precise Ir analyses are necessary in order to confirm this.

Simulated Bromoform emission and concentration using the ocean biogeochemistry model MPIOM/HAMOCC forced by 6-hourly NCEP data

Bromoform (CHBr3) is one important precursor of atmospheric reactive bromine species that are involved in ozone depletion in the troposphere and stratosphere. In the open ocean bromoform production is linked to phytoplankton that contains the enzyme bromoperoxidase. Coastal sources of bromoform are higher than open ocean sources. However, open ocean emissions are important because the transfer of tracers into higher altitude in the air, i.e. into the ozone layer, strongly depends on the location of emissions. For example, emissions in the tropics are more rapidly transported into the upper atmosphere than emissions from higher latitudes. Global spatio-temporal features of bromoform emissions are poorly constrained. Here, a global three-dimensional ocean biogeochemistry model (MPIOM-HAMOCC) is used to simulate bromoform cycling in the ocean and emissions into the atmosphere using recently published data of global atmospheric concentrations (Ziska et al., 2013) as upper boundary conditions. Our simulated surface concentrations of CHBr3 match the observations well. Simulated global annual emissions based on monthly mean model output are lower than previous estimates, including the estimate by Ziska et al. (2013), because the gas exchange reverses when less bromoform is produced in non-blooming seasons. This is the case for higher latitudes, i.e. the polar regions and northern North Atlantic. Further model experiments show that future model studies may need to distinguish different bromoform-producing phytoplankton species and reveal that the transport of CHBr3 from the coast considerably alters open ocean bromoform concentrations, in particular in the northern sub-polar and polar regions.

Geochemistry of bulk sediment from the Cape Basin

A technique for onsite application of X-ray fluorescence (XRF) spectrometry to samples from sediment cores aboard a research vessel was developed and tested. The method is sufficiently simple, precise, and fast to be used routinely for high-resolution analyses of depth profiles as well as surface samples. Analyses were performed with the compact high-performance energy-dispersive polarisation X-ray fluorescence (EDPXRF) analyser Spectro Xepos. Contents of the elements Si, Ti, Al, Fe, Mn, Mg, Ca, K, Sr, Ba, Rb, Cu, Ni, Zn, P, S, Cl and Br were simultaneously determined on 200-225 samples of each core within 24 h of recovery. This study presents a description of the employed shipboard preparation and analysis technique, along with some example data. We show land-based datasets that support our decisions to use powder samples and to reduce the original measuring time for onboard analyses. We demonstrate how well the results from shipboard measurements for the various elements compare with the land-based findings. The onboard geochemical data enabled us to establish an element stratigraphy already during the cruise. Correlation of iron, calcium and silicon enrichment trends with an older reference core provided an age model for the newly retrieved cores. The Spectro Xepos instrument performed without any analytical and technical difficulties which could have been caused by rougher weather conditions or continuous movement and vibration of the research vessel. By now, this XRF technique has been applied during three RV Meteor cruises to approximately 5,000 Late Quaternary sediment samples from altogether 23 gravity cores, 25 multicorer cores and two box cores from the eastern South Atlantic off South Africa/Namibia and the eastern Atlantic off NW Africa.

Physico-chemical parameters of sediment core PG1975-1 (09-Tik-05) from a Tundra Lake, Northeastern Siberia

The relationships between thermokarst activity, limnogeological processes and climate change in the Siberian Arctic are not well understood. The objective of this paper is to identify the factors controlling the patterns of deposition, using grain size distribution, organic content, elemental composition and mineralogical composition of a 137-cm long sediment core with a maximum age of ~10.9 cal. kyr BP from Lake El'gene-Kyuele in the tundra of northeastern Siberia. Eight fine sand layers are attributed to depositional events associated with thaw slump activity acting upon orthogonally oriented patterns of ice-wedge networks in the ice-rich permafrost on the NW margin of the lake catchment. Sr/Rb ratios, which correspond to the total feldspar and illite content, serve as high-resolution grain size proxies. The Br content relates to the total organic carbon content, and the Fe/Mn ratio reflects the degree of oxidisation. Our results indicate a relationship between repeated phases of fine sand input and retrogressive thaw slumping dependent on hydroclimate variability and orthogonally oriented ice-wedge networks within the catchment.