Fluxes of iron and manganese across the sediment–water interface under various redox conditions

Fluxes of dissolved forms of iron and manganese across the sediment–water interface were studied in situ in the Gulf of Finland and the Vistula Lagoon (Baltic Sea), and in the Golubaya Bay (Black Sea) from 2001 to 2005. Fluxes were measured using chamber incubations, and sediment cores were collected and sliced to assess the porewater and solid phase metal distribution at different depths. Measured and calculated benthic fluxes of manganese and iron were directed out of sediment for all sites and were found to vary between 70–4450 and 5–1000 µmole m^− 2 day^− 1 for manganese and iron, respectively. The behavior of the studied metals at various redox conditions in the near-bottom water and in the sediment was the main focus in this study. Our results show the importance of bottom water redox conditions for iron fluxes. We measured no fluxes at oxic conditions, intermediate fluxes at anoxic conditions (up to 200 μmole m^− 2 day^− 1) and high fluxes at suboxic conditions (up to 1000 μmole m^− 2 day^− 1). Total dissolved iron fluxes were generally dominated by iron(II). Contribution of iron(III) to the total iron flux did not exceed 20%. Obtained fluxes of manganese at all studied regions showed a linear correlation (r² = 0.97) to its concentration in the porewater of the top sediment layer (0–5 mm) and did not depend on dissolved oxygen concentrations of bottom water. Organically complexed iron and manganese were in most cases not involved in the benthic exchange processes.     

On lipid surface films on the sea. I. A simple method for sampling and studies of composition

A method for collection of surface films on the sea has been developed and tested at various places along the Swedish West Coast. Considerable amounts of lipids on the sea surface were found even when no seaslicks were observed. Triglycerides, free fatty acids, and wax esters are the dominating constituents, and there are characteristic deviations in the fatty-acid patterns compared to the corresponding lipids dissolved in the sub-surface water. Organochlorine residues, phthalic acid esters and heavy metals also occur in considerable amounts.     

Modelling the Baltic Sea ocean climate on centennial time scale: temperature and sea ice

This study considers the possible use of different kinds of forcing datasets in Baltic Sea ocean climate modelling on centennial time scales, in particular for the past half millennium. We demonstrate that high-quality station data of the past century and gridded multi-proxy reconstructions for the past 500 years can be used with great success but with various levels of detail. We also demonstrate that output data from the state-of-the-art global climate model EcHo-G are not suitable for modelling the Baltic Sea ocean climate. Two climate properties were studied: the annual maximum ice extent (MIB) and the vertically and horizontally integrated annual water temperature. Centennial time scale results indicate that the seventeenth and nineteenth centuries were the coldest centuries, while the 1690s were the coldest decade and 1695 the coldest year in the last 500 years. The results also indicate that the twentieth century was the warmest century with the least MIB of the last 500 years. On a decadal time scale, the 1990s, 1930s and 1730s were the warmest decades and comparable in terms of both water temperature and MIB. The year 1989 had the minimum observed MIB of only 52,000 km², implying that the Baltic Sea has been partly ice covered in all winters of the past half millennium. Even though different climate forcing mechanisms may operate on the climate system today compared to over the last half millennium, this study cannot clearly state that the region is experiencing climate change outside the natural limits of the past 500 years.     

Moon and Earth : compositional differences inferred from siderophiles,volatiles, and alkalis in basalts

We have compared RNAA analyses of 18 trace elements in 25 low-Ti lunar and 10 terrestrial oceanic basalts. According to Ringwood and Kesson, the abundance ratio in basalts for most of these elements approximates the ratio in the two planets.Volatiles (Ag, Bi, Br, Cd, In, Sb, Sn, Tl, Zn) are depleted in lunar basalts by a nearly constant factor of 0.026 ± 0.013, relative to terrestrial basalts. Given the differences in volatility among these elements, this constancy is not consistent with models that derive the Moon's volatiles from partial recondensation of the Earth's mantle or from partial degassing of a captured body. It is consistent with models that derive planetary volatiles from a thin veneer (or a residuum) of C-chondrite material; apparently the Moon received only 2.6% of the Earth's endowment of such material per unit mass.Chalcogens (Se and Te) have virtually constant and identical abundances in lunar and terrestrial basalts, probably reflecting saturation with Fe(S, Se, Te) in the source regions.Siderophiles show diverse trends. Ni is relatively abundant in lunar basalts (4 × 10^?3 × Cl-chondrites), whereas Ir, Re, Ge, Au are depleted to 10^?4?10^?5× Cl. Except for Ir, these elements are consistently enriched in terrestrial basalts: Ni 3 × , Re 370 ×, Ge 330 × , Au 9 × . This difference apparently reflects the presence of nickel-iron phase in the lunar mantle, which sequesters these metals. On Earth, where such metal is absent, these elements partition into the crust to a greater degree. Though no lunar mantle rock is known, an analogue is provided by the siderophile-rich dunite 72417 (~0.1% metal) and the complementary, siderophile-poor troctolite 76535. The implied metal-siderophile distribution coefficients range from 10⁴ to 10⁶, and are consistent with available laboratory data.The evidence does not support the alternative explanation advanced by Ringwood—that Re was volatilized during the Moon's formation, and is an incompatible element (like La or W⁴⁺) in igneous processes. Re is much more depleted than elements of far greater volatility: (Re/U)_Cl～- 4 × 10^?6 vs (T1/U)_Cl = 1.3 × 10^?4, and Re does not correlate with La or other incompatibles.Heavy alkalis (K, Rb, Cs) show increasing depletion with atomic number. Cs/Rb ratios in lunar basalts, eucrites, and shergottites are 0.44, 0.36, and 0.65 × Cl, whereas the value for the bulk Earth is 0.15–0.26. These ratios fall within the range observed in LL and E6 chondrites. supporting the suggestion that the alkali depletion in planets, as in chondrites, was caused by localized remelting of nebular dust (= chondrule formation). Indeed, the small fractionation of K, Rb and Cs, despite their great differences in volatility, suggests that the planets, like the chondrites, formed from a mixture of depleted and undepleted material, not from a single, partially devolatilized material.     

Backtracking of Noble Gas Measurements Taken in the Aftermath of the Announced October 2006 Event in North Korea by Means of PTS Methods in Nuclear Source Estimation and Reconstruction

The announced October 2006 nuclear test explosion in the Democratic People’s Republic of Korea (DPRK) has been the first real test regarding the technical capabilities of the verification system built up by the Vienna-based Provisional Technical Secretariat (PTS) of the Comprehensive Nuclear-Test-Ban Treaty Organization (CTBTO) to detect and locate a nuclear test event. This paper enhances the resolution of the DPRK events’ xenon source reconstruction published by Saey et al. (2007, “A long distance measurement of radioxenon in Yellowknife, Canada, in late October 2006”, GRL, Vol. 34, L20802) that was based solely on radio-xenon measurements taken at the remote radionuclide station in Yellowknife, Canada by involving additional measurements taken by a mobile noble gas system deployed quite close to the event location in the Republic of Korea (ROK). Moreover the horizontal resolution of the forward and backward atmospheric transport modelling methods applied for the source scenario reconstruction has been enhanced appropriately to reflect the considerably shorter source-receptor distances examined in comparison to the previously published source reconstruction. It is shown that the ¹³³Xe measurements in Yellowknife could register ¹³³Xe traces from the nuclear explosion during the first 3 days after the event, while the mobile measurements were rather sensitive to releases during days 2–4 after the explosion. According to the analysis, the most likely source scenario would consist of an initial (possibly up to 21 h delayed) venting of 1 × 10^?15 Bq ¹³³Xe during the first 24 h, followed by a two orders of magnitude weaker seepage during the following 3 days. Both measurements corroborate the scenario of a rather rapid venting and soil diffusion of the ¹³³Xe yielded during the explosion. While the Swedish mobile measurements were crucial to enhancement of the reconstruction of the source scenario, given the installation status of the IMS xenon network at the time of the event, a sensitivity analysis revealed that the fully developed network would have been able to detect ¹³³Xe traces from the Korean explosion at a number of stations and allowed for an even better constraint on the release function. The station Ussuriysk, Russia, being in operation in 2006, would have registered ¹³³Xe within 1 day and with a three orders of magnitudes stronger signal compared to the detection at Yellowknife.     

A study on the fractionation of organic matter in natural water by ultrafiltration techniques

Diaflo ultrafilters have been studied for the fractionation of organic matter in natural water. One method for their use, including pretreatment, is described. The filter retention is not only depending on the weight of the molecule but also on the charge as shown by experiments with dyestuffs and inorganic ions. For pure solutions of phosphate and nitrate the retentions were 77 and 27% respectively. Filter UM 2, with a nominal molecular weight cutoff at 1,000, retained coloured and total organic matter to 94 and 91% respectively. UM 10 (10,000) retained coloured matter to 88%. Through filtrations the binding of calcium to organic in water was found to be 1 to 10%.     

Precipitation and evaporation budgets over the Baltic Proper: observations and modelling

Precipitation and evaporation budgets over the Baltic Sea were studied in a concerted project called PEP in BALTEX (Pilot study of Evaporation and Precipitation in the Baltic Sea), combining extensive field measurements and modelling efforts. Eddy-correlation-measurements of turbulent heat flux were made on a semi-continuous basis for a 12 month period at four well-exposed coastal sites in the Baltic Proper (the main basin of the Baltic Sea). Precipitation was measured at land-based sites with standard gauges and on four merchant ships travelling between Germany and Finland with the aid of specially designed ship rain gauges (SRGs). The evaporation and precipitation regime of the Baltic Sea was modelled for a 12 month period by applying a wide range of numerical models: the operational atmospheric High Resolution Limited Area Model (HIRLAM, Swedish and Finnish versions), the German atmospheric REgional-scale MOdel, REMO, the operational German Europe Model (only precipitation), the oceanographic model PROBE-Baltic, and two models that use interpolation of ground-based data, the Swedish MESAN model of SMHI and a German model of IFM-GEOMAR Kiel. Modelled precipitation was compared with SRG measurements on board the ships. A reasonable correlation was obtained, but the regional-scale models and MESAN gave some 20% higher precipitation over the sea than is measured. Bulk parameterisation schemes for evaporation were evaluated against measurements. A constant value of C_HN and C_EN with wind speed, underestimated large fluxes of both sensible and latent heat flux. The limited area models do not resolve the influence of the height of the marine boundary layer in coastal zones and the entrainment (on the surface fluxes), which may explain the observed low correlations between modelled and measured latent heat fluxes. Estimates of evaporation, E, and precipitation, P, for the entire Baltic Proper were made with several models for a 12 month period. While the annual variation was well represented by all predictions, there are still important differences in the annual means. Evaporation ranges from 509 to 625 mm year^-1 and precipitation between 624 and 805 mm year^-1 for this particular 12 month period. Taking the results of model verification from the present study into account, the best estimate of P-E is about 100 ± 50 mm for this particular 12 month period. But the annual mean of P-E varies considerably from year to year. This is reflected in simulations with the PROBE-Baltic model for an 18 year period, which gave 95 mm year^-1 for the 12 month period studied here and 32 mm year^-1 as an average for 18 years.     

Extinct I129 in C3 chondrites

Eight C3 chondrites were examined by the I¹²⁹Xe¹²⁹ dating method, to see whether their IXe “ages” (better, initial $\text{I}{}^{129}\text{I}{}^{127}$ratios ≡ R₀) correlate with any other properties. The R₀'s range from 1.60 × 10^?4 to 1.09 × 10^?4, corresponding to IXe ages from 2.0 Myr before to 6.7 Myr after Murchison magnetite. Three C3O's (Lancé, Felix, Ornans) have essentially indistinguishable R₀'s of (1.41 ± 0.13) to (1.17 ± 0.10) × 10^?4; the fourth C3O, Warrenton, is undatable owing to homogenization of radiogenic and trapped Xe.Four C3V's show a distinct spread: Vigarano and Grosnaja are highest [R₀ = (1.60 ± 0.07) and (1.57 ± 0.14) × 10^?4], Mokoia is intermediate, and Kaba is lowest [R₀ = (1.38 ± 0.06) and (1.09 ± 0.10) × 10^?4]. Literature values for Allende place it near Kaba. These R₀'s correlate inversely with 4 other properties: I-, Br-, and Cd-content, and olivine composition, both percent mean deviation (PMD) and proportion of iron-poor olivine grains (≤2% fayalite).It is difficult to accept the ～9 Myr spread in R₀ as a true age, reflecting either nebular or parent-body processes. This time span is more than an order of magnitude longer than the lifetime of the solar nebula inferred from astronomical evidence. Nor does the degree of thermal metamorphism, which is slight for C3's anyway, correlate with R₀. A more plausible interpretation is that the variations in R₀ reflect mainly isotopic heterogeneity of iodine. The simplest model that accounts for the correlations with R₀ involves mixing of two iodine components in the solar nebula, associated with gas and grains, respectively. The second, of lower $\text{I}{}^{129}\text{I}{}^{127}$ ratio, predominated at later times and thus became enriched in late-formed meteorites, along with other volatiles such as Cd and Br. The low Fe content and large PMD of olivine may reflect either less metamorphism owing to shallow location in the parent body, or greater reduction of Fe²⁺ during chondrule formation.