Fast Oxidation Reaction of Nitrite by Dissolved Oxygen in the Freezing Process in the Tropospheric Aqueous Phase

Nitrite oxidation in the tropospheric aqueous phase by freezing was evaluated by freezing a field sample. Nitrite oxidation by dissolved oxygen in the freezing process is much faster than by other oxidation processes, such as reactions with ozone, hydrogen peroxide or dissolved oxygen in an aqueous solution at pHs 3 to –6. At pH 4.5 and 25°C, the lifetime of nitrite in the aqueous phase is ca. 1 hr in oxidation by ozone (6×10^-10 mol dm^-3), ca. 10 hr in oxidation by H₂O₂ (2×10^-4 mol dm^-3), and 7.5 hr (Fischer and Warneck, 1996) in photodissociation at midday in summer. Under the same conditions at a temperature below 0°C, the lifetime of nitrite in the freezing process is estimated as ca. 2 sec when the droplets are frozen within a second. The reaction by freezing is affected by the presence of salts, such as NaCl or KCl, or orgnaic compounds, such as methanol or acetone. The results of freezing a field rain or fog sample showed that nitrite oxidation proceeds below pH 6, and the conversion ratio of nitrate from nitrite increases with decreasing pH. The oxidation of nitrite by freezing was also observed in freezing fog particles generated by an ultrasonic humidifier. The ratios of the concentrations of ions in the winter sample to those in the summer sample (or those in the fog sample) were almost the same values. However, the concentration of nitrite in the winter sample was lower than that estimated by the ratios of other ions. From the present study, it seems that the freezing process plays an important role in the nitrite sink process in the tropospheric aqueous phase.     

A study of Mg and K isotopes in Allende CAIs: Implications to the time scale for the multiple heating processes

Abstract— The measurements of magnesium and potassium isotopic compositions of refractory minerals in Allende calcium‐aluminum‐rich inclusions (CAIs), 7R‐19–1, HN3–1, and EGG3 were taken by secondary ion mass spectrometry (SIMS). The 7R‐19–1 contains ¹⁶O‐rich and ¹⁶O‐poor melilite grains and define a single isochron corresponding to an initial ²⁶Al/²⁷Al ratio of (6.6 ± 1.3) × 10^?5. The Al‐Mg isochron, O isotope measurements and petrography of melilite in 7R‐19–1 indicate that ¹⁶O‐poor melilite crystallized within 0.4 Myr after crystallization of ¹⁶O‐rich melilite, suggesting that oxygen isotopic composition of the CAI‐forming region changed from ¹⁶O‐rich to ¹⁶O‐poor within this time interval. The ¹⁶O‐poor melilite is highly depleted in K compared to the adjacent ¹⁶O‐rich melilite, indicating evaporation during remelting of 7R‐19–1. We determined the isochron for ⁴¹Ca‐⁴¹K isotopic systematics in EGG3 pyroxene with (4.1 ± 2.0) × 10^?9 (2s?) as an initial ratio of ⁴¹Ca/⁴⁰Ca, which is at least two times smaller than the previous result (Sahijipal et al. 2000). The ratio of ⁴¹Ca/⁴⁰Ca in the EGG3 pyroxene grain agrees within error with the value obtained by Hutcheon et al. (1984). No evidence for the presence of ⁴¹K excess (decay product of a short‐lived radionuclide ⁴¹Ca) was found in 7R‐19–1 and HN3–1. We infer that the CAI had at least an order of magnitude lower than canonical ⁴¹Ca/⁴⁰Ca ratio at the time of the CAI formation.     

Nuclide analyses of rare earth elements of the Oklo uranium ore samples: a new method to estimate the neutron fluence

Isotopic ratios and abundances of all REE in two Oklo ore samples have been measured. We have succeeded in developing a new method to estimate the neutron fluence, the conversion factor of uranium and the average neutron energy (or temperature) based on Gd and U isotopic ratios. This new calculation is found to be useful in evaluating those parameters for the natural nuclear reactors at Oklo. Comparison is made between the neutron fluence values evaluated by our new method employing Gd isotopes and a previous one [11] employing Sm and Nd isotopes. The relative agreement becomes better with the increase of fluence. A relationship between the abundances of fissiongenic nuclides of La, Ce, Nd, Sm, and Gd and their mass numbers is also presented.     

Gas capture and rare gas retention by accreting planets in the solar nebula

In this paper, the physico-chemical effects of the nebula gas on the planets are reviewed from a standpoint of planetary formation in the solar nebula.The proto-Earth growing in the nebula was surrounded by a primordial atmosphere with a solar chemical composition and solar isotopic composition. When the mass of the proto-Earth was greater than 0.3 times the present Earth mass, the surface was molten because of the blanketing effect of the atmosphere. Therefore, the primordial rare gasses contained in the primordial atmosphere dissolved into the molten Earth material without fractionation and in particular the dissolved neon is expected to be conserved in the present Earth material. Hence, if dissolved neon with a solar isotopic ratio is discovered in the Earth material, it will indicate that the Earth was formed in the nebula and that the dissolved rare gases were one of the sources which degassed to form the present atmosphere.     

Pressure and temperature dependence of cation distribution in Mg-Mn olivine

Synthetic (Mg_0.51, Mn_0.49)₂SiO₄ olivine samples are heat-treated at three different pressures; 0, 8 and 12 GPa, all at the same temperature (～500° C). X-ray structure analyses on these single crystals are made in order to see the pressure effect on cation distribution. The intersite distribution coefficient of Mg and Mn in M1 and M2 sites, K _D = (Mn/Mg) _M1/(Mn/Mg) _M2, of these samples are 0.192 (0 GPa), 0.246 (8 GPa) and 0.281 (12 GPa), indicating cationic disordering with pressure. The small differences of cell dimensions between these samples are determined by powder X-ray diffraction. Cell dimensions b and c decrease, whereas a increases with pressure of equilibration. Cell volume decreases with pressure as a result of a large contraction of the b cell dimension. The effect of pressure on the free energy of the cation exchange reaction is evaluated by the observed relation between the cell volume and the site occupancy numbers. The magnitude of the pressure effect on cation distribution is only a fifth of that predicted from the observed change in volume combined with thermodynamic theory. This phenomenon is attributed to nonideality in this solid solution, and nonideal parameters are required to describe cation distribution determined in the present and previous experiments. We use a five-parameter equation to specify the cationic equilibrium on the basic of thermodynamic theory. It includes one energy parameter of ideal mixing, two parameters for nonideal effects, one volume parameter, and one thermal parameter originated from the lattice vibrational energy. The present data combined with some of the existing data are used to determine the five parameters, and the cation distribution in Mg-Mn olivine is described as a function of temperature, pressure, and composition. The basic framework of describing the cationic behavior in olivine-type mineral is worked out, although the result is preliminary: each of the determined parameters is not accurate enough to enable us to make a reliable prediction.     

Transfer of60Co from midwater squid to sperm whales

Sperm whales are notable squid-eaters. They feed mainly on medium to large-sized cephalopods at midwater levels and defecate near the surface. This suggests the existence of an upward transport of⁶⁰Co by sperm whales from the mesopelagic zone (150–1,200 m). To elucidate this squid-whale route for this artificial radionuclide,⁶⁰Co content was determined in squid and in predator whales captured by commercial whaling. In the Cephalopoda livers⁶⁰Co levels of 30–500 mBq kg^–1 wet were found and in the viscera of Odontoceti (toothed whales) 15–40 mBq kg^–1 wet. About 0.3% of⁸⁰Co ingested was estimated to be retained in a 23-year-old male sperm whale. In the livers of Bryde's whales,⁶⁰Co levels of 40–80 mBq kg^–1 wet were detected, but not in euphausiids and sardines, their possible prey. The level of Co in sperm whales was nearly the same as in Bryde's whales. Specific radioactivity⁶⁰Co/⁵⁹Co in mBq µg^–1 was several times higher in sperm whale (1.1–1.6) than in cephalopods (0.19–0.77). Eating prey with a high content of⁶⁰Co in the 1960's may have contributed to the present body burden in sperm whales with a long-life span. However, the origin of⁶⁰Co in Bryde's whales is unknown.     

ESR diagram: a method to distinguish vitrinite macerals

It has been found that samples consisting of a homogeneous vitrinite show a good ESR correlation of spin concentration with geothermal parameters and that a graph of ESR line width vs g-value can be useful in the identification of the maceral and the determination of the coalification rank.     

The theory of the nutation for the rigid earth model at the second order

We perform a complete reconstruction of the series of the nutation for a rigid Earth model with the use of the very accurate theories ELP2000 and VSOP82 for the motion of the Moon and the planets respectively, in such a way that all the individual contributions up to 0.005 mas should be taken. This implies the introduction of the planetary effects, of the influence of second-order parts of the potential of the Earth (J3, triaxiality), and some improvements due to an extension of the theory at the second order. All this increase notably the number of coefficients to be taken in account, and modifies also in a significant way the value of some of them.     

Large-Eddy Simulation of Pollutant Removal from a Three-Dimensional Street Canyon

Large-eddy simulations were conducted to investigate the mechanism of pollutant removal from a three-dimensional street canyon. Five block configurations with aspect ratios (building height to length) of 1, 2, 4, 8 and $\infty $ were used to create an urban-like array. A pollutant was released from a ground-level line source at the centre of the target canyon floor. For smaller aspect ratios, the relative contribution of the turbulent mass flux to net mass flux at the roof level, which was spatially averaged along the roof-level ventilation area, was closer to unity, indicating that turbulent motions mainly affected pollutant removal from the top of the canyon. As aspect ratio increased, the relative contribution became smaller, owing to strong upwind motions. However, the relative contribution again reached near unity for the infinite aspect ratio (i.e. a two-dimensional street canyon) because of lowered lateral flow convergence. At least 75 % of total emissions from the three-dimensional street canyon were attributable to turbulent motions. Pollutant removal by turbulent motions was related to the coherent structures of low-momentum fluid above the canyons. Though the coherent structure size of the low-momentum fluid differed, the positions of low-momentum fluid largely corresponded to instantaneous high concentrations of pollutant above the target canyon, irrespective of canyon geometry.     

Biogenic carbon flows through the planktonic food web of the Amundsen Gulf (Arctic Ocean): A synthesis of field measurements and inverse modeling analyses

Major pathways of biogenic carbon (C) flow are resolved for the planktonic food web of the flaw lead polynya system of the Amundsen Gulf (southeast Beaufort Sea, Arctic Ocean) in spring-summer 2008. This period was relevant to study the effect of climate change on Arctic marine ecosystems as it was characterized by unusually low ice cover and warm sea surface temperature. Our synthesis relied on a mass balance estimate of gross primary production (GPP) of 52.5 ± 12.5 g C m⁻² calculated using the drawdown of nitrate and dissolved inorganic C, and a seasonal f-ratio of 0.64. Based on chlorophyll a biomass, we estimated that GPP was dominated by phytoplankton (93.6%) over ice algae (6.4%) and by large cells (>5 μm, 67.6%) over small cells (<5 μm, 32.4%). Ancillary in situ data on bacterial production, zooplankton biomass and respiration, herbivory, bacterivory, vertical particle fluxes, pools of particulate and dissolved organic carbon (POC, DOC), net community production (NCP), as well as selected variables from the literature were used to evaluate the fate of size-fractionated GPP in the ecosystem. The structure and functioning of the planktonic food web was elucidated through inverse analysis using the mean GPP and the 95% confidence limits of every other field measurement as lower and upper constraints. The model computed a net primary production of 49.2 g C m⁻², which was directly channeled toward dominant calanoid copepods (i.e. Calanus hyperboreus 20%, Calanus glacialis 10%, and Metridia longa 10%), other mesozooplankton (12%), microzooplankton (14%), detrital POC (18%), and DOC (16%). Bacteria required 29.9 g C m⁻², a demand met entirely by the DOC derived from local biological activities. The ultimate C outflow comprised respiration fluxes (82% of the initial GPP), a small sedimentation (3%), and a modest residual C flow (15%) resulting from NCP, dilution and accumulation. The sinking C flux at the model limit depth (395 m) supplied 60% of the estimated benthic C demand (2.8 g C m⁻²), suggesting that the benthos relied partly on other C sources within the bottom boundary layer to fuel its activity. In summary, our results illustrate that the ongoing decline in Arctic sea ice promotes the growth of pelagic communities in the Amundsen Gulf, which benefited from a ∼80% increase in GPP in spring-summer 2008 when compared to 2004 – a year of average ice conditions and relatively low GPP. However, 53% of the secondary production was generated within the microbial food web, the net ecological efficiency of zooplankton populations was not particularly high (13.4%), and the quantity of biogenic C available for trophic export remained low (6.6 g C m⁻²). Hence it is unlikely that the increase in lower food web productivity, such as the one observed in our study, could support new harvestable fishery resources in the offshore Beaufort Sea domain.