Atomistic simulation of the mechanisms of noble gas incorporation in minerals

Atomistic simulations have been carried out to investigate the mechanisms of noble gas incorporation in minerals using both the traditional two-region approach and the “supercell” method. The traditional two-region approach has been used to calculate defect energies for Ne, Ar, Kr and Xe incorporation in MgO, CaO, diopside and forsterite in the static limit and at one atmosphere pressure. The possibilities of noble gas incorporation via both substitution and interstitial mechanisms are studied. The favored mechanism varies from mineral to mineral and from noble gas to noble gas. In all minerals studied, the variation of the solution energies of noble gas substitution with atomic radius appears approximately parabolic, analogous to those for 1⁺, 2⁺, 3⁺ and 4⁺ trace element incorporation on crystal lattice sites. Noble gas solution energies thus also fall on a curve, similar to those previously observed for cations with different charges, but with much lower curvature.The “supercell” method has been used to investigate the pressure dependence of noble gas incorporation in the same systems. Results indicate a large variation of the solubility of the larger noble gases, Kr and Xe with pressure. In addition, explicit simulation of incorporation at the (0 0 1) surface of MgO shows that the solubility of the heavier noble gases may be considerably enhanced by the presence of interfaces.     

Surface evolution of dissolving minerals investigated with a kinetic Ising model

In natural weathering systems, both the chemistry and the topography of mineral surfaces change as rocks and minerals equilibrate to surface conditions. Most geochemical research has focused on changes in solution chemistry over time; however, temporal changes in surface topography may also yield information about rates and mechanisms of dissolution. We use stochastic dissolution simulations of a regular 2-D lattice with reaction mechanisms defined in terms of nearest neighbor interactions to elucidate how the surface area and reactivity of a crystal evolve during dissolution. Despite the simplicity of the model, it reproduces key features observed or inferred for mineral dissolution. Our model results indicate that: (i) dissolving surfaces reach a steady-state conformation after sufficient dissolution time, (ii) linear defects cause surface area and dissolution rate to vary in concert with one another, (iii) sigmoidal and non-sigmoidal rate vs. free-energy of reaction (ΔG_rxn) behavior can be rationalized in terms of the multiple steps occurring during dissolution, and (iv) surface roughness as a function of ΔG_rxn is highly sensitive to the reaction mechanism. When simulated times to reach steady-state are compared to published time series rate data using suitable scaling, good agreement is found for silicate minerals while the model significantly over-predicts the duration of the transient for Fe and Al oxides. The implication of our simple model is that many aspects of mineral dissolution behavior, including approach to steady-state, sigmoidal vs. non-sigmoidal rate vs. ΔG_rxn behavior, and development of rougher surfaces in conditions further from equilibrium can be explained by nearest neighbor interactions and simple Kossel-type models where reactivity of a surface is defined in terms of perfect surface, step, and kink sites.     

Comparison of arsenic concentrations in simultaneously-collected groundwater and aquifer particles from Bangladesh,India, Vietnam,and Nepal

One of the reasons the processes resulting in As release to groundwater in southern Asia remain poorly understood is the high degree of spatial variability of physical and chemical properties in shallow aquifers. In an attempt to overcome this difficulty, a simple device that collects groundwater and sediment as a slurry from precisely the same interval was developed in Bangladesh. Recently published results from Bangladesh and India relying on the needle-sampler are augmented here with new data from 37 intervals of grey aquifer material of likely Holocene age in Vietnam and Nepal. A total of 145 samples of filtered groundwater ranging in depth from 3 to 36 m that were analyzed for As (1–1000 μg/L), Fe (0.01–40 mg/L), Mn (0.2–4 mg/L) and S (0.04–14 mg/L) are compared. The P-extractable (0.01–36 mg/kg) and HCl-extractable As (0.04–36 mg/kg) content of the particulate phase was determined in the same suite of samples, in addition to Fe(II)/Fe ratios (0.2–1.0) in the acid-leachable fraction of the particulate phase. Needle-sampler data from Bangladesh indicated a relationship between dissolved As in groundwater and P-extractable As in the particulate phase that was interpreted as an indication of adsorptive equilibrium, under sufficiently reducing conditions, across 3 orders of magnitude in concentrations according to a distribution coefficient of 4 mL/g. The more recent observations from India, Vietnam and Nepal show groundwater As concentrations that are often an order of magnitude lower at a given level of P-extractable As compared to Bangladesh, even if only the subset of particularly reducing intervals characterized by leachable Fe(II)/Fe >0.5 and dissolved Fe >0.2 mg/L are considered. Without attempting to explain why As appears to be particularly mobile in reducing aquifers of Bangladesh compared to the other regions, the consequences of increasing the distribution coefficient for As between the particulate and dissolved phase to 40 mL/g for the flushing of shallow aquifers of their initial As content are explored.     

Geochronology of Pliocene volcanism in the Dzhavakheti Highland (the Lesser Caucasus). Part 1: Western part of the Dzhavakheti Highland

Isotopic-geochronological study of the Pliocene magmatic activity in western part of the Dzhavakheti Highland (northwestern region of the Lesser Caucasus) is carried out. The results obtained imply that the Pliocene magmatic activity lasted in this part of the highland approximately 2 million years from 3.75 to 1.75–1.55 Ma. As is established, the studied volcanic rocks correspond in composition mostly to K-Na subalkaline and more abundant normal basalts. Time constraints of main phases in development of basic volcanism within the study region are figured out. We assume that individual pulses of silicic to moderately silicic volcanism presumably took place in the Dzhavakheti Highland about 3.2 and 2.5 Ma ago.     

Dynamics of an elastically moored floating body by the three-dimensional infinite element method

The three-dimensional problem of the dynamics of a moored floating object under the action of regular waves is solved numerically as a boundary value problem by use of the finite-infinite element method. The cross-sectional shape of the floating body and the mooring arrangements may all be arbitrary. The mathematical formulations of the problem and procedures of the numerical method are presented in this paper. A corresponding computer program WALOAD has been developed, which is capable of computing wave forces on fixed and floating structures. Numerical computations using this program could give very accurate results, even though rather coarse meshes were used. The program is easy to use and is readily applicable in many practical situations.     

Variation of reactivity of particulate and sedimentary organic matter along the Zhujiang River Estuary

To investigate organic matter source and reactivity in the Zhujiang River (Pearl River)Estuary and its adjacent areas, particulate organic carbon (POC), particulate hydrolysable amino acids (PHAA), and Chl a during two cruises in July 1999 and July 2000 were measured. The highest POC and PHAA concentration was observed in the waters with maximum Chl a. The spectra distribution,relative content (dry weight in milligram per gram), PHAA-C% POC and other indicators such as the ratios of amino acids vs. amino sugars (AA/AS) and glucosamine vs. galactosamine (Glum/Gal) suggested that particulate amino acids in the water column and sediments in the Zhujiang River Estuary were mainly derived from biogenic processes rather than transported from terrestrial erosion. In inner estuary where high turbidity was often observable, organic matter was mainly contributed by re-suspension of bottom sediments with revealed zooplankton, microbial reworked characteristics, which suggest that these organic matters were relatively “old“. In the estuarine brackish region, organic matter in water column is mainly contributed by relatively fresh, easily degradable phytoplankton derived organic matter.During physical - biological processes within the eastuary, organic matter derived from phytoplankton was subjected to alteration by zooplankton grazing and bacterial reworking.     

Robust adaptive control of underactuated ships on a linear course with comfort

This paper addresses an important problem in ship control application—the robust stabilization of underactuated ships on a linear course with comfort. Specifically, we develop a multivariable controller to stabilize ocean surface ships without a sway actuator on a linear course and to reduce roll and pitch simultaneously. The controller adapts to unknown parameters of the ship and constant environmental disturbances induced by wave, ocean current and wind. It is also robust to time-varying environmental disturbances, time-varying change in ship parameters and other motions of the ship such as surge and heave. The roll and pitch can be made arbitrarily small while the heading angle and sway are kept to be in reasonably small bounds. The controller development is based on Lyapunov’s direct method and backstepping technique. A Lipschitz continuous projection algorithm is used to update the estimate of the unknown parameters to avoid the parameters’ drift due to time-varying environmental disturbances. Simulations on a full-scale catamaran illustrate the effectiveness of our proposed controller.     

冰心中的气候环境记录与全球变化研究

冰心是高分辨地记录全球变化的主要信息载体之一。本文总结了冰心中提取古气候和古环境信息的系列记录，包括同位素、微量气体、阴阳离子、微粒、生物和有机质等。着重讨论了由这些记录提取的古气候和古环境变化方面的研究进展，并提出了今后的研究重点。