Computational methods for fitting statistical distribution models of multi-site binding equilibria

Statistical distribution models of multi-site binding equilibria have potential applicability in the study of acid-base and metal complexation chemistry of humic substances in soils, sediments, and natural waters. A mathematical derivation is presented for the general continuous model for the case of proton binding; computational methods are described for fitting numerically the parameters in such models. Among models considered are those based on nontruncated, truncated, and bimodal (mixed) distributions. Specific emphasis is placed on Gaussian distribution models.     

Nitrogen and sulfur species in Antarctic aerosols at Mawson,Palmer Station,and Marsh (King George Island)

High volume bulk aerosol samples were collected continuously at three Antarctic sites: Mawson (67.60° S, 62.50° E) from 20 February 1987 to 6 January 1992; Palmer Station (64.77° S, 64.06° W) from 3 April 1990 to 15 June 1991; and Marsh (62.18° S, 58.30° W) from 28 March 1990, to 1 May 1991. All samples were analyzed for Na⁺, SO ₄ ^2– , NO ₃ ^– , methanesulfonate (MSA), NH ₄ ⁺ ,²¹⁰Pb, and⁷Be. At Mawson for which we have a multiple year data set, the annual mean concentration of each species sometimes vary significantly from one year to the next: Na⁺, 68–151 ng m^–3; NO ₃ ^– , 25–30 ng m^–3; nss SO ₄ ^2– , 81–97 ng m^–3; MSA, 19–28 ng m^–3; NH ₄ ⁺ , 16–21 ng m^–3;²¹⁰Pb, 0.75–0.86 fCi m^–3. Results from multiple variable regression of non-sea-salt (nss) SO ₄ ^2– with MSA and NO ₃ ^– as the independent variables indicates that, at Mawson, the nss SO ₄ ^2– /MSA ratio resulting from the oxidation of dimethylsulfide (DMS) is 2.80±0.13, about 13% lower than our earlier estimate (3.22) that was based on 2.5 years of data. A similar analysis indicates that the ratio at Palmer is about 40% lower, 1.71±0.10, and more comparable to previous results over the southern oceans. These results when combined with previously published data suggest that the differences in the ratio may reflect a more rapid loss of MSA relative to nss SO ₄ ^2– during transport over Antarctica from the oceanic source region. The mean²¹⁰Pb concentrations at Palmer and Marsh and the mean NO ₃ ^– concentration at Palmer are about a factor of two lower than those at Mawson. The²¹⁰Pb distributions are consistent with a²¹⁰Pb minimum in the marine boundary layer in the region of 40°–60° S. These features and the similar seasonalities of NO ₃ ^– and²¹⁰Pb at Mawson support the conclusion that the primary source regions for NO ₃ ^– are continental. In contrast, the mean concentrations of MSA, nss SO ₄ ^2– , and NH ₄ ⁺ at Palmer are all higher than those at Mawson: MSA by a factor of 2; nss SO ₄ ^2– by 10%; and NH ₄ ⁺ by more than 50%. However, the factor differences exhibit substantial seasonal variability; the largest differences generally occur during the austral summer when the concentrations of most of the species are highest. NH ₄ ⁺ /(nss SO ₄ ^2– +MSA) equivalent ratios indicate that NH₃ neutralizes about 60% of the sulfur acids during December at both Mawson and Palmer, but only about 30% at Mawson during February and March.     

SETTLING PROPERTIES OF COHESIVE AND NON-COHESIVE PARTICULATE MIXTURES IN WATER

1. INTRODUCTIONAs a wide range of size distirbution including usually a certain POrtion of cohesive material is thecommon feature of the sediment constituting hyperconcentrated flows. it is desirable to study the settling properties of mixtures of cohesive and non--cohesjve sediment particles at high concentrations.Past studies on the settling of discrete particles in a suspension of fine cohesjve sediment is scarcein the literature. The Sediment Research Laboratory of Tsinghua Universi…     

The importance of atmospheric input of terrestrial organic material to deep sea sediments

The concentrations of lipids were determined in atmospheric particle, gas and rain samples collected from the tropical North Pacific to assess lipid sources, transport mechanisms and fluxes to the ocean surface. Four lipid compound classes (aliphatic hydrocarbons, fatty alcohols, fatty acid esters, and salts) all unequivocally show a terrestrial vascular plant source. These aerosol lipids originate from wind erosion of Asian and American soils and direct emission from vegetation. The major fluxes result from rain rather than dry deposition. These fluxes are large enough to have a major potential impact on the inventory of terrestrially derived lipid material found in deep-sea sediments. This has been showm for n-alkanes, fatty alcohols, fatty acids, total lipids and for organic carbon. By comparing atmospheric and sediment trap fluxes with sediment accumulation rates, it is suggested that some biogenic terrestrial material is more protected from degradation than marine-derived material.     

Transport and deposition of suspended particles in saturated porous media: hydrodynamic effect

A laboratory study was undertaken to determine the transport and deposition rate of suspended particles in columns of saturated porous media (gravel and glass beads), where the porous media were subjected to steady-state flow. Silt particles with a mode of 14 μm diameter (used as the suspended particles) and fluorescein (as the conservative tracer) were injected into the columns in short pulses. The breakthrough curves were competently described with the analytical solution of a convection–dispersion equation with a first-order deposition rate. The experiments were performed using different flow rates. The suspended particle size distribution, the porous media, and the flow rates themselves were the main factors retained in this study to investigate the mechanisms governing the transport and deposition kinetics in detail. The results showed the existence of a flow rate, beyond which suspended particles travel faster than the conservative tracer. A decrease of the deposition rate of suspended particles beyond a critical flow velocity was also observed. Such behaviour led to consideration of the couple hydrodynamic-gravity forces at high flow rates. As the hydrodynamic force increases, particle deposition rates are reduced due to the effect of hydrodynamic forces inhibiting the deposition.     

山西义兴寨金矿床金矿物颗粒的产出及其成矿动力学意义

山西义兴寨金矿床的金主要呈包体金和裂隙金两种产出状态.文章根据成矿地球化学动力学理论,论证了金元素在含矿断裂发生脆性破裂和脆-韧性扩张活动中析出的化学反应类型,以及受反应动力学条件的制约,形成矿石中金不同产出状态的规律.指出热液矿床中普遍存在的包体金为热液成矿早期阶段断裂发生脆性破裂和成矿流体沸腾,导致快速反应结晶的产物;而裂隙金和晶隙金为成矿晚期金等矿质在流体中残余富集,同时成矿断裂再次发生脉动破裂,即成矿热力学演化与有利的构造动力学因素耦合作用的结果.得出金矿物颗粒的产出状态具有成矿动力学意义的结论.     

EFFECT OF FLOW CONDITIONS ON 3D MOVEMENT CHARACTERISTICS OF PARTICLES

1 INTRODUCTION The mechanism of particle movement in the flow is one of basic problems of sediment transport research. The conventional measurement approaches usually disturb the structure of the flow, consequently inducing errors. With the development of…     

Residual strength of slip zones of large landslides in the Three Gorges area, China

Slip zones of the large landslides in the Three Gorges area are commonly composed of fine-grained soils with substantial amount of coarse-grained particles, particularly gravel-sized particles. In this study, residual strength of the soils from slip zones of these landslides were examined in relation to their index properties based on a survey of 170 landslides. It was found that laboratory-determined residual friction angle using gravel-free fraction of the disturbed soils from the slip zones was closely related to clay content, liquid limit and plasticity index. On the other hand, in-situ residual friction angle of these soils (i.e. including gravel fraction) showed very weak correlations with clay content and Atterberg limits, but was largely dependent on gravel and fines (clays + silts) contents, increasing with gravels and decreasing with fines, and displayed strong linear correlation with the ratio of gravel to fines contents. These observations indicate that among the index properties, clay content and Atterberg limits can be used to estimate residual strength of the soils finer than 2 mm, but they are not appropriate evaluate the residual strength of the soils containing considerable amount of gravel-sized particles. For the latter, particle size distribution (particularly the ratio of gravel to fines contents) appears to be a useful index. Additionally, it was found that there was no identifiable correlation between relative abundance of individual major clay minerals and residual friction angles of both gravel-free fraction of disturbed and in-situ soils, suggesting that influence of clay minerals on residual strength of these soils can not be simply evaluated based on their abundance.     

Mineral magnetic and physical properties of surficial sediments and onshore samples from the southern basin of Lake Baikal, Siberia

Results of lithostratigraphic and mineral magnetic analysis of two surficial sediment cores (21 cm and 45 cm in length) collected from the Southern basin of Lake Baikal at a water depth of 1390 m, are presented. The sediments have been measured for a wide range of mineral magnetic parameters in order to assess their value in the identification of turbidite layers. Particle size and geochemical data are also presented and these explain some of the down core variations in magnetic mineralogy. It is suggested that changes in the particle size frequency distributions down core may be related to fossil diatom shells. One of the cores has been dated using ²¹⁰Pb. The sediment cores were cross-correlated using low frequency magnetic susceptibility (f) and these cores can also be correlated with a nearby core collected earlier in 1992. Changes in the magnetic parameters of lf, IRMs and HIRM₂₁₀ suggest that there are significant changes in the concentration of ferrimagnetic minerals in the sediment cores, indicating changing sediment sources and/or increasing concentrations of spheroidal carbonaceous particles and the dissolution of minerals through reduction below the oxidised layer within the sediment core.     

The importance of energetic particle precipitation on the chemical composition of the middle atmosphere

An assessment is made of the relative contribution of certain classes of energetic particle precipitation to the chemical composition of the middle atmosphere with emphasis placed on the production of odd nitrogen and odd hydrogen species and their subsequent role in the catalytic removal of ozone. Galactic cosmic radiation is an important source of odd nitrogen in the lower stratosphere but since the peak energy deposition occurs below the region where catalytic removal of O₃ is most effective, it is questionable whether this mechanism is important in the overall terrestrial ozone budget. The precipitation of energetic solar protons can periodically produce dramatic enhancement in upper stratospheric NO. The long residence time of NO in this region of the atmosphere, where catalytic interaction with O₃ is also most effective, mandates that this mechanism be included in future modelling of the global distribution of O₃. Throughout the mesosphere the precipitation of energetic electrons from the outer radiation belt (60°70°) can sporadically act as a major local source of odd hydrogen and odd nitrogen leading to observable O₃ depletion. Future satellite studies should be directed at simultaneously measuring the precipitation flux and the concomitant atmosphere modification, and these results should be employed to develop more sophisticated models of this important coupling.