Stoichiometry among bioactive trace metals in the Chukchi and Beaufort Seas

The distribution of Al, Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb in seawater was investigated in the Chukchi and Beaufort Seas of the western Arctic Ocean in September 2000. The unfiltered and filtered seawater samples were used for determination of total dissolvable metal (TDM) and dissolved metal (DM), respectively. The concentration of labile particulate metal (LPM) was estimated with the difference between that of TDM and DM. The concentrations of TDAl, TDMn, TDFe, TDCo and TDPb varied substantially in the study area. The high concentrations occurred at stations near the Bering Strait, in the Mackenzie delta, and above reductive sediments on the shelf and slope. These elements were mostly dominated by labile particulate species, such as Fe?CMn oxides and species adsorbed on terrestrial clay. DCo was correlated with DMn over the study area (r?=?0.78, n?=?135), and the slope of the regression line was 27 times higher at a pelagic station than at a shelf station. TDNi, TDCu, TDZn and TDCd showed relatively small variations and were generally dominated by dissolved species. There was a moderate correlation between DCd and phosphate for all samples (r?=?0.79), whereas there were no significant correlation between the other DMs and nutrients. TDNi and TDCu showed a remarkable linearity for most stations except those near the Bering Strait (R ²?=?0.95, n?=?126). These results suggest that biogeochemical cycling including uptake by phytoplankton and remineralization from settling particles has only minor control over the distribution of trace metals in this area. Using the present data, the annual input of bioactive trace metals form the Bering Strait and the Mackenzie River was estimated. Also, the trace metal compositions of major water masses were evaluated. The dissolved elemental ratio was P:Al:Mn:Fe:Co:Ni:Cu:Zn:Cd?=?1:1.2?×?10^?2:4.4?×?10^?4:1.4?×?10^?3:3.7?×?10^?5:3.7?×?10^?3:1.4?×?10^?3:4.5?×?10^?3:2.2?×?10^?4 for Canada Basin deep water (CBDW). This ratio was significantly different from that for Pacific deep water and Bering Sea water, suggesting substantial modification of the trace metal compositions of seawater in the study area.     

Manganiferous schists and their origin,Hidaka Mountains,Hokkaido, Japan

Manganiferous quartz-mica schists (4 m in stratigraphic thickness) overlie epidote amphibolite in the Chiroro River area, Hidaka Mountains, Hokkaido. The schist layers have a considerable range of A/F ratios and bulk oxidation ratios which vary from 21.5 to 100. Manganese contents are from 4 to 30 times higher than that of the average shale with 0.09% MnO. The schists are essentially quartz-white mica-biotite-Mn garnet-tourmaline-±epidote-magnetite assemblages. A highly oxidized layer (5–8 cm thick) 95 cm above the epidote amphibolite contact is characterized by viridine-piemontite-spessartine-Mn white mica-Mn tourmaline-Ti-Mn haematite indicative of both high initial manganese content and very high f _O2 conditions of recrystallization.Viridine contains up to 17 mol% Mn³⁺SiO₅ and coexists with piemontite with between 13.6 and 15.4 wt% Mn₂O₃. Mn-poor-Fe-rich (Ps₃₂) epidote occurs in the less oxidized schist enclosing the viridine-piemontite bearing seam. Garnets vary widely in composition with end member variations (mol%) of Spess_22.9–80.5; And_0.2–11.7; Alm_1.1–57.1; Pyr_2.0–12.2; Gross_7.0–49.0. The more manganiferous garnets occur in rocks with higher oxidation ratios while almandiferous varieties occur in schists with low oxidation ratios. Biotite ranges from green to red-brown varieties (increasing Ti and Fe) with Mg/ (Mg+Fe) ratios varying from 56 to 48. Ten to fifteen percent octahedral R²⁺ is replaced by Al indicating a trend towards eastonite-siderophyllite. The white micas deviate only slightly from dioctahedral stoichiometry but have up to 25% of octahedral sites occupied by Fe, Mg and to a lesser extent Mn and Ti as R²⁺ Si⁴⁺2Al³⁺ and in highly oxidized rocks as (Fe,Mn)³⁺Al³⁺. The white mica in the highly oxidized viridine-piemontite schist is pale pinkishorange, exhibits reverse pleochroism, and has between 0.30 and 0.43 wt% Mn₂O₃.There is a close comparison, both in terms of stratigraphic thickness and Fe-Mn variation, between the Chiroro schist sequence and many oceanic cores so that the bulk chemistry and mineralogy of the pelitic schists is largely an extension of the original Eh-pH conditions of hemipelagic sedimentation and post-depositional adjustments during diagenesis. The thin viridine-piemontite bearing schist is correlated with an oxidized, Fe-Mn rich layer commonly found in present day oceanic cores. The viridine presumably formed by reaction of original ferro-manganese microgranules and clay minerals. Halmrolytic alteration of the underlying metabasalt resulted in leaching of Mn and Fe (in particular) into the overlying sediments and the formation of concentrations of haematite — manganese oxide — Mn garnet along the schist-epidote amphibolite contact.Estimation of the P-T conditions of metamorphism from the phase relations and compositions in the epidote amphibolite associated with the manganiferous schist gives T °C = 530560 and a minimum P _fluid > 3 kb which corresponds to the epidote amphibolite facies of Barrovian-type terrains.This paper is dedicated to Professor Kenzo Yagi on the occasion of his retirement from the Chair of Mineralogy, Department of Geology and Mineralogy, Hokkaido University, Sapporo, Japan     

An experimental study on impact-induced alterations of planetary organic simulants

The present study systematically investigates shock-induced alteration of organic simulants of planetary bodies (OSPBs) as a function of peak shock pressure and temperature by impact experiments. Our results show that the composition and structure of OSPBs are unchanged upon impacts at peak pressures ≤~5 GPa and temperatures ≤~350 °C. On the other hand, these are dramatically changed upon impacts at >7–8 GPa and > ~400 °C, through loss of hydrogen-related bonds and concurrent carbonization, regardless of the initial compositions of OSPBs. Compared with previous results on static heating of organic matter, we suggest that shock-induced alteration cannot be distinguished from static heating only by Raman and infrared spectroscopy. Our experimental results would provide a proxy indicator for assessing degree of shock-induced alteration of organic matter contained in carbonaceous chondrites. We suggest that a remote-sensing signature of the 3.3–3.6 μm absorption due to hydrogen-related bonds on the surface of small bodies would be a promising indicator for the presence of less-thermally-altered (i.e., <350 °C) organic matter there, which will be a target for landing to collect primordial samples in sample-return spacecraft missions, such as Hayabusa2 and OSIRIS-REx.