943 resultados para ION CHEMISTRY
Resumo:
Fission fragment mass distributions were measured in heavy-ion induced fission of 238U. The mass distributions changed drastically with incident energy. The results are explained by a change of the ratio between fusion and quasifission with nuclear orientation. A calculation based on a fluctuation dissipation model reproduced the mass distributions and their incident energy dependence. Fusion probability was determined in the analysis. Evaporation residue cross sections were calculated with a statistical model for the reactions of 30Si+238U and 34S+238U using the obtained fusion probability in the entrance channel. The results agree with the measured cross sections of 263,264Sg and 267,268Hs, produced by 30Si+238U and 34S+238U, respectively. It is also suggested that sub-barrier energies can be used for heavy element synthesis.
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The development and improvement of MC-ICP-MS instruments have fueled the growth of Lu–Hf geochronology over the last two decades, but some limitations remain. Here, we present improvements in chemical separation and mass spectrometry that allow accurate and precise measurements of 176Hf/177Hf and 176Lu/177Hf in high-Lu/Hf samples (e.g., garnet and apatite), as well as for samples containing sub-nanogram quantities of Hf. When such samples are spiked, correcting for the isobaric interference of 176Lu on 176Hf is not always possible if the separation of Lu and Hf is insufficient. To improve the purification of Hf, the high field strength elements (HFSE, including Hf) are first separated from the rare earth elements (REE, including Lu) on a first-stage cation column modified after Patchett and Tatsumoto (Contrib. Mineral. Petrol., 1980, 75, 263–267). Hafnium is further purified on an Ln-Spec column adapted from the procedures of Münker et al. (Geochem., Geophys., Geosyst., 2001, DOI: 10.1029/2001gc000183) and Wimpenny et al. (Anal. Chem., 2013, 85, 11258–11264) typically resulting in Lu/Hf < 0.0001, Zr/Hf < 1, and Ti/Hf < 0.1. In addition, Sm–Nd and Rb–Sr separations can easily be added to the described two-stage ion-exchange procedure for Lu–Hf. The isotopic compositions are measured on a Thermo Scientific Neptune Plus MC-ICP-MS equipped with three 1012 Ω resistors. Multiple 176Hf/177Hf measurements of international reference rocks yield a precision of 5–20 ppm for solutions containing 40 ppb of Hf, and 50–180 ppm for 1 ppb solutions (=0.5 ng sample Hf 0.5 in ml). The routine analysis of sub-ng amounts of Hf will facilitate Lu–Hf dating of low-concentration samples.
Resumo:
Mineralization of organic matter and the subsequent dissolution of calcite were simulated for surface sediments of the upper continental slope off Gabon by using microsensors to measure O2, pH, pCO2 and Ca2+ (in situ), pore-water concentration profiles of NO3-, NH4+, Fe2+, and Mn2+ and SO42- (ex situ), as well as sulfate reduction rates derived from incubation experiments. The transport and reaction model CoTReM was used to simulate the degradation of organic matter by O2, [NO3]-, Fe(OH)3 and [SO4]2-, reoxidation reactions involving Fe2+ and Mn2+, and precipitation of FeS. Model application revealed an overall rate of organic matter mineralization amounting to 50 µmol C cm**-2 yr**-1, of which 77% were due to O2, 17% to [NO3]- and 3% to Fe(OH)3 and 3% to [SO4]2-. The best fit for the pH profile was achieved by adapting three different dissolution rate constants of calcite ranging between 0.01 and 0.5% d-1 and accounting for different calcite phases in the sediment. A reaction order of 4.5 was assumed in the kinetic rate law. A CaCO3 flux to the sediment was estimated to occur at a rate of 42 g m**-2 yr**-1 in the area of equatorial upwelling. The model predicts a redissolution flux of calcite amounting to 36 g m**-2 yr**-1, thus indicating that ~90% of the calcite flux to the sediment is redissolved.
Resumo:
To improve quantitative interpretation of ice core aeolian dust records a systematic methodical comparison has been made involving methods of water-insoluble particle counting (Coulter Counter and laser-sensing particle detector), soluble ions (ion chromatography, IC, and continuous flow analysis, CFA), elemental analysis (inductively coupled plasma mass spectroscopy, ICP-MS, at pH 1 and after full acid digestion), and water-insoluble elemental analysis (proton induced X-ray emission, PIXE). Ice core samples covering the last deglaciation have been used from the EPICA Dome C (EDC) and the EPICA Dronning Maud Land (EDML) ice cores. All methods correlate very well amongst each other. The ratios of glacial age concentrations to Holocene concentrations, which are typically a factor ~100, differ significantly between the methods, but differences are limited to a factor < 2 for most methods with insoluble particles showing the largest change. The recovery of ICP-MS measurements depends on the digestion method and is different for different elements and during different climatic periods. EDC and EDML samples have similar dust composition, which suggests a common dust source or a common mixture of sources for the two sites. The analysed samples further reveal a change of dust composition during the last deglaciation.
Resumo:
A 181 m deep ice core drilled in 1994/95 on the south dome of Berkner Island, Antarctica, was analyzed for stable isotopes, major ions and microparticle concentrations. Samples for ion chromatography were prepared by using a novel technique of filling decontaminated sample from a device for continuous ice-core melting directly into the sample vials. The core was dated through identification of volcanic horizons and interpolative layer counting. The core, together with a similar core from the north dome, reveals a 1000 year history of relatively stable climate. Temporal variations in the two cores deviate from each other owing to changing patterns of regional-scale circulation; the best correspondence between them is found for MSA-. delta18O, accumulation rate and a sea-salt proxy show only negligible correlation, which suggests a complex meteorological setting. Increasing annual accumulation is observed for the last 100 years. A period of increased sea-salt concentrations started around AD 1405, as has also been observed in other cores. Microparticle concentrations are on average 1220 particles (>=1.0 ?m diameter)/mL; they are enhanced from AD 1200 to 1350, possibly because of a higher atmospheric mineral dust load or because local volcanic activity was stronger than previously thought. Microparticles and NH4+show marked but multiple and very irregular sub-annual peaks; long-term stacking of 1 year data intervals yields seasonal maxima in austral spring or mid-summer, respectively. Post-depositional redistribution was observed for MSA, NO3- and F- at volcanic horizons.
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Concentrations of major ions, silicate and nutrients (total N and P) were measured in samples of surface water from 28 lakes in ice-free areas of northern Victoria Land (East Antarctica). Sixteen lakes were sampled during austral summers 2001/02, 2003/04, 2004/05 and 2005/06 to assess temporal variation in water chemistry. Although samples showed a wide range in ion concentrations, their composition mainly reflected that of seawater. In general, as the distance from the sea increased, the input of elements from the marine environment (through aerosols and seabirds) decreased and there was an increase in nitrate and sulfate concentrations. Antarctic lakes lack outflows and during the austral summer the melting and/or ablation of ice cover, water evaporation and leaching processes in dry soils determine a progressive increase in water ion concentrations. During the five-year monitoring survey, no statistically significant variation in the water chemistry were detected, except for a slight (hardly significant) increase in TN concentrations. However, Canonical Correspondence Analysis (CCA) indicated that other factors besides distance from the sea, the presence of nesting seabirds, the sampling time and percentage of ice cover affect the composition of water in Antarctic cold desert environments.
Resumo:
We carried out short term pCO2/pH perturbation experiments in the coastal waters of the South China Sea to evaluate the combined effects of seawater acidification (low pH/high pCO2) and solar UV radiation (UVR, 280-400 nm) on photosynthetic carbon fixation of phytoplankton assemblages. Under photosynthetically active radiation (PAR) alone treatments, reduced pCO2 (190 ppmv) with increased pH resulted in a significant decrease in the photosynthetic carbon fixation rate (about 23%), while enriched pCO2 (700 ppmv) with lowered pH had no significant effect on the photosynthetic performance compared to the ambient level. The apparent photosynthetic efficiency decreased under the reduced pCO2 level, probably due to C-limitation as well as energy being diverged for up-regulation of carbon concentrating mechanisms (CCMs). In the presence of UVR, both UV-A and UV-B caused photosynthetic inhibition, though UV-A appeared to enhance the photosynthetic efficiency under lower PAR levels. UV-B caused less inhibition of photosynthesis under the reduced pCO2 level, probably because of its contribution to the inorganic carbon (Ci)-acquisition processes. Under the seawater acidification conditions (enriched pCO2), both UV-A and UV-B reduced the photosynthetic carbon fixation to higher extents compared to the ambient pCO2 conditions. We conclude that solar UV and seawater acidification could synergistically inhibit photosynthesis.
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We present the first study of the effects of ocean acidification on settlement of benthic invertebrates and microfauna. Artificial collectors were placed for 1 month along pH gradients at CO2 vents off Ischia (Tyrrhenian Sea, Italy). Seventy-nine taxa were identified from six main taxonomic groups (foraminiferans, nematodes, polychaetes, molluscs, crustaceans and chaetognaths). Calcareous foraminiferans, serpulid polychaetes, gastropods and bivalves showed highly significant reductions in recruitment to the collectors as pCO2 rose from normal (336-341 ppm, pH 8.09-8.15) to high levels (886-5,148 ppm) causing acidified conditions near the vents (pH 7.08-7.79). Only the syllid polychaete Syllis prolifera had higher abundances at the most acidified station, although a wide range of polychaetes and small crustaceans was able to settle and survive under these conditions. A few taxa (Amphiglena mediterranea, Leptochelia dubia, Caprella acanthifera) were particularly abundant at stations acidified by intermediate amounts of CO2 (pH 7.41-7.99). These results show that increased levels of CO2 can profoundly affect the settlement of a wide range of benthic organisms.
Resumo:
Production (abundance and biomass) and net calcification rates of the coccolithophorid Pleurochrysis carterae under different partial pressures of CO2 (pCO2) were examined using short (15, 24 and 39 h), long (7 d) and dark (7 d) incubation experiments. Short incubations were conducted at ambient, 500 and 820 ppm pCO2 levels in natural seawater that was enriched with nutrients and inoculated with P. carterae. Long incubations were conducted at ambient and 1200 ppm pCO2 levels in natural seawater (0.2 µm filtered as well as unfiltered) that was enriched with nutrients and inoculated with P. carterae. Dark incubations were conducted at ambient and 1200 ppm pCO2 in unfiltered seawater that was inoculated with P. carterae. The abundance and biomass of coccolithophorids increased with pCO2 and time. The abundance and biomass of most noncalcifying phytoplankton also increased, and were hardly affected by CO2 inputs. Net calcification rates were negative in short incubations during the pre-bloom phase regardless of pCO2 levels, indicating dissolution of calcium carbonate. Further, the negative values of net calcification in short incubations became less negative with time. Net calcification rates were positive in long incubations during blooms regardless of pCO2 level, and the rate of calcification increased with pCO2. Our results show that P. carterae may adapt to increased (~1200 ppm) pCO2 level with time, and such increase has little effect on the ecology of noncalcifying groups and hence in ecosystem dynamics. In dark incubations, net calcification rates were negative, with the magnitude being dependent on pCO2 levels.