H+与Cl-缔合作用的进一步探讨

众所周知,在电解质溶液及电化学研究中,人们总是把通常浓度的盐酸和高氯酸当作非缔合电解质[1-6]。近期,继文献[7]报道了用电导法测定Cl-与Na+和K+的缔合常数以后,K.S.Johnson和R.M.Pytkowicz认为H+与Cl-有缔合,他们求算了其化学计量缔合常数,并在其改进的海水化学模型中考虑了H+、Na+、K+与Cl-的缔合作用[8,9]。然而,苏联作者对在海水中形成MgCl+和CaCl+离子对提出了异议[10]。我们用有液界电池电动势法和无液界电池电动势法试图测定HCl°的化学计量缔合常数,根据实验结果着重探讨了H+与Cl-有无缔合的问题。     

海洋化学中的直线自由能关系——Ⅱ.海水中元素的液-固分配

本文第1部分中,我们用一种比较简捷的方法,导出了海洋化学中直线自由能关系。通过海洋化学中若干重要体系的实验数据,验证了海洋化学中直线自由能关系的客观存在。它们是海水元素溶存形式(海水化学模型)中A-Cl,A-OH,A-SO_3,A-CO,A-F等离子对稳定常数之间的直线自由能关系,海水中金属和有机物质(hum)相互作用的稳定常数与海水化学模型的稳定常数之间的直线自由能关系。本文中我们进一步研究海水     

高氯酸水溶液活度系数和水的渗透系数的测定

近代发展的离子选择电极为电化学研究提供了方便,用其组成无液界电池可测定一些电解质溶液的活度系数。通常浓度的高氯酸具有非缔合电解质的性质,它对于电化学溶液理论及电分析化学实验研究均有一定的意义。在海水化学模型专题研究中,曾利用其非缔合性质探讨一些离子的缔合作用。高氯酸的活度系数已有报道,但早期用     

海水中碳酸根与固体粒子的相互作用

本文研究了海水中碳酸根在固体粒子上的吸附。碳酸根在各种因素颗粒物上的吸附程度上大小顺序为：赤铁矿〉δ－ＭｎＯ２〉水锰矿〉ＳｉＯ２,最大吸附量可达到约２ｍｇＣ／ｇ吸附剂,且最大吸附值均在天然海水ｐＨ（ｐＨ８）左右。在低ＰＨ时,碳酸根对ＮａＣｌ介质中砷酸根的吸附没有影响,在高ｐＨ时,则降低了砷酸根在固体颗粒物上的吸附量,因此碳酸根的存在对其他阴离子的吸附会产生竞争作用。     

高氯酸水溶液活度系数和水的渗透系数的测定

近代发展的离子选择电极为电化学研究提供了方便，用其组成无液界电池可测定一些电解质溶液的活度系数。通常浓度的高氯酸具有非缔合电解质的性质，它对于电化学溶液理论及电分析化学实验研究均有一定的意义。在海水化学模型专题研究中，曾利用其非缔合性质探讨一些离子的缔合作用[1]。     

浮游有孔虫壳体重量的古海洋学应用

海洋沉积物中浮游有孔虫壳体重量同时受到上层海洋钙化过程和深海碳酸钙溶解作用的影响，是一种潜在的古海洋代用指标。基于全球大洋表层沉积物的指标现代过程校准，发现当深海碳酸根离子饱和度<20μmol·kg^-1，溶解作用开始显著影响浮游有孔虫壳体重量。易溶种的壳体重量对碳酸根离子饱和度的响应更加敏感，可以作为可靠的深海碳酸根离子饱和度代用指标。当深海碳酸根离子饱和度>20μmol·kg^-1，浮游有孔虫壳体重量可反映其钙化程度。基于该指标的古海洋学研究揭示了冰期旋回中浮游有孔虫钙化过程主要响应海水碳酸盐系统和温度变化；上新世以来太平洋深海碳酸根离子饱和度演化主要受控于海平面、南大洋冰盖/海冰和全球温盐环流变化。浮游有孔虫壳体重量指标为探索海洋碳循环演化提供了有力工具。     

南海东北部海区碳酸钙的饱和面、溶跃面和补偿深度

南海东北部碳酸钙地球化学研究得出:上层海水中方解石饱和度450—550％,文石饱和度250—350％.300m以深下层海水方解石与文石饱和度和深度的对数直线相关.深层水中二氧化碳含量0.03mmo1·dm~-3,碳酸根含量0.094mmol·dm~(-3),碳酸氢根含量2.35mmol·dm~(-3)总二氧化碳2.48mmo1·dm~(-3);方解石的饱和面1630m,溶跃面3000m,补偿深度4600m,文石饱和面435m,补偿深度1000m.     

近十年来我国海洋化学研究的若干进展

本文对近十年来海洋化学的若干新进展作了总结,主要包括下述7方面:(1)海洋调查,包括中国近海、太平洋和南极等;(2)海水中微量元素-固体粒子的相互作用和界面分级离子/配位子交换理论;(3)有机物对液-固界面交换的影响和S-型曲线左右移动规律;(4)海水化学模型发展的三个新趋势;(5)海水中金属的络合容量和金属-天然有机配位体络合物的条件稳定常数;(6)海洋有机化学和海洋生物化学;(7)结论,对海洋化学发展的四个特点作了分析和讨论。     

海水中银-卤化银固溶体参比电极

根据化学海洋学中海水组成保守性和固-液平衡原理,以及海水中银的溶存形式,计算并合成了与天然海水中卤离子呈热力学平衡的卤化银固溶体。以该固溶体作为活性材料制成的全固态银-卤化银电极,对海水中氯离子活度具有理想的Nernst响应。在天然海水中浸泡近四年(1986.1—1989.11)的结果表明,该电极具有良好的化学稳定性和电化学稳定性且不存在电势漂移和光敏现象,是比常规的银-氯化银电极更为理想的参比电极,已成功地用作海洋构筑物阴极保护系统的长寿命参比电极。     

海水中微量元素存在形式的模拟计算

本文用模拟数值方法，引用Ｄａｖｉｅｓ离子强度校正方程和热力学稳定常数，计算了海水中Ｃｕ、Ｐｂ、Ｃｄ和Ｈｇ的无机和有机络合物的百分比含量，从理论上探讨了重金属化学形式的规律。     

Microbial Biomass and Organic Nutrients in the Deep-Sea Sediments of the Central Indian Ocean Basin

In order to assess the impact of deep-sea mining on the in situ benthic life, we measured the microbial standing stock and concentration of organic nutrients in the deep-sea sediments of the Central Indian Ocean Basin in the Indian pioneer area. Sediments were collected using box core and grab samples during September 1996. The total bacterial numbers ranged from 10 10 -10 11 cells per g -1 dry weight sediment. There was a marginal decrease in the number of bacteria from surface to 30 cm depth, though the subsurface section registered a higher number than did the surface. The highest numbers were encountered at depths of 4-8 cm. The retrievable number of bacteria were two orders less in comparison with the direct total counts of bacteria. An almost homogeneous distribution of bacteria, total organic carbon, living biomass, and lipids throughout the depth of cores indicates active microbial and benthic processes in the deep sea sediments. On the other hand, a uniform distribution of total counts of bacteria, carbohydrates, and total organic carbon in all the cores indicates their stable nature and suggests that they can serve as useful parameters for long-term monitoring of the area after the benthic disturbance. Further studies on temporal variability in this region would not only verify the observed norms of distribution of these variables but would also help to understand restabilization processes after the simulated benthic disturbance.     

Assessing the Validity of Seismo-Acoustic Predictor Equations for Obtaining Seabed and Sub-Surface Sediment Physical Properties

The interdependence between the seismo-acoustic properties of a marine sediment and its geotechnical/physical parameters has been known for many years, and it has been postulated that this should allow the extraction of geotechnical information from seismic data. Though in the literature many correlations have been published for the surficial layer, there is a lack of information for greater sediment depths. In this article, a desktop study on a synthetic seafloor model illustrates how the application of published near-surface prediction equations to subsurface sediments (up to several tens of meters burial depth) can lead to spurious predictions. To test this further, acoustic and geotechnical properties were measured on a number of sediment core samples, some of which were subjected to loading in acoustically-equipped consolidation cells (oedometers) to simulate greater burial depth conditions. For low effective pressures (representing small burial depths extending to around 10 meters subsurface), the general applicability of established relationships was confirmed: the prediction of porosity, bulk density, and mean grain size from acoustic velocity and impedance appears generally possible for the investigated sedimentary environments. As effective pressure increases through, the observed relationships deviate more and more from the established ones for the near-surface area. For the samples tested in this study, in some instances increasing pressure even resulted in decreasing velocities. There are several possible explanations for this abnormal behavior, including the presence of gas, overconsolidation, or bimodal grain size distribution. The results indicate that an appropriate depth correction must be introduced into the published prediction equations in order to obtain reliable estimates of physical sediment properties for greater subsurface depths.     

A Review of Some Environmental Issues Affecting Marine Mining

This article reviews information recently available from existing marine and coastal mining for responses to environmental issues affecting marine mining at different depths. It is particularly but not exclusively concerned with those issues affecting seabed biodiversity impact and recovery. Much information has been gathered in the past 10 years from shallow mining operations for construction aggregate, diamonds, and gold, from coastal mines discharging tailings to shallow and deep water, and from experimental deep mining tests. The responses to issues identified are summarized in a series of eight tables intended to facilitate site-specific consideration. Since impacts can spread widely in the surface mixing layer SML, and can affect the biologically productive euphotic zone, the main issues considered arise from the depth of mining relative to the SML of the sea. Where mining is below the SML, the issue is whether it is environmentally better to bring the extraction products to the surface vessel for processing (and waste discharge), or to process the extraction products as much as possible on the seabed. Responses to the issues need to be sitespecific, and dependent on adequate preoperational environmental impact and recovery prediction. For deep tailings disposal from a surface vessel, there are four important environmental unknowns: (1) the possible growth of "marine snow" (bacterial flocs) utilizing the enormous quantities of fine tailings particles (hundreds or thousands of metric tons per day) as nuclei for growth, (2) the possibility that local keystone plankton and nekton species may migrate diurnally down to and beyond the depth of deep discharge and hence be subjected to tailings impact at depth, (3) the burrow-up capability of deep benthos and their ability to survive high rates of tailings deposition, and (4) the pattern and rate of dispersion of a tailings density current through the deep water column from discharge point to seabed. Actions to obtain relevant information in general and site-specifically are suggested.     

Increased Particle Fluxes at the INDEX Site Attributable to Simulated Benthic Disturbance

Particle fluxes were measured 7 m above the sea bottom during the predisturbance, disturbance, and postdisturbance periods by using time series sediment traps attached to seven deep-sea moorings deployed in the INDEX experiment site in the Central Indian Basin. The predisturbance particle fluxes varied between 22.3 to 55.1 mg m -2 day -1 . Increased and variable particle fluxes were recorded by the sediment traps during the disturbance period. The increase observed was 0.5 to 4 times more than the background predisturbance fluxes. The increases in particle fluxes (~4 times) recorded by the sediment trap located in the southwestern direction (DMS-1) were the greatest, which could be the result of preferential movement of resuspended particles generated during the deep-sea benthic disturbance along the general current direction prevailing in this area during the experimental period. Also, the traps located closer to the disturbance area recorded greater fluxes than did the traps far away, across the Deep Sea Sediment Resuspension System path. This variability in recorded particle fluxes by the traps around the disturbance area clearly indicates that physical characteristics such as grain size and density of the resuspended particles produced during the disturbance had an important effect on particle movement. The postdisturbance measurements during ~5 days showed a reduction in particle fluxes of ~50%, indicating rapid particle settlement.     

海上大直径钢管桩打桩过程中桩周土强度弱化研究

海上大直径钢管桩打桩过程中,桩周土体受到强烈扰动而发生强度弱化,掌握桩周土体强度弱化规律对于准确预测打桩过程、保证工程安全具有重要意义。为研究土体强度弱化规律,开展了环剪试验模拟打桩对桩周土体的扰动,测试土体强度随剪切速率的变化规律,建立了描述土体强度弱化规律的拟合公式,引入到打桩分析软件中。研究结果表明：土体的强度折减程度不仅与土体本身的性质有关还受到土体的埋深和剪切速率的影响,埋深越深土体强度折减程度越低,剪切速率越高土体强度折减越高,在打桩分析中可采用这里推荐的线性折减方法来模拟不同深度处土体强度的折减规律。     

Geoacoustic Inversion via Genetic Algorithm and Its Application to Manganese Sediment Identification

An acoustic inversion method using a wide-band signal and two near field receivers is proposed and applied to multiple layered seabed models including a manganese sediment. The inversion problem can be formulated into a probabilistic model comprised of signals, a forward model, and additive noise. The forward model simulates wide-band signals, such as chirp signals, and is chosen to be the source-waveletconvolution plane wave modeling method. The wavelet matching technique, using weighted least-squares fitting, estimates the sediment sound-speed and thickness on which determination of the possible numerical ranges for a priori uniform distribution is based. The genetic algorithm is applied to a global optimization problem to find a maximum a posteriori solution for determined a priori search space. Here the object function is defined by an L 2 norm of the difference between measured and modeled signals. Not only the marginal pdf but also its statistics are calculated by numerical evaluation of integrals using the samples selected during importance sampling process of the genetic algorithm.     

Determination of In Situ Sediment Shear Strength from Advanced Piston Corer Pullout Forces

The advanced piston corer (APC) has been used by the Ocean Drilling Program since 1985 for recovering soft sediments from the ocean floor. The pullout force measured on extracting the core barrel from the sediment is shown to correlate with the average shear strength of the sediment core measured in the ship's laboratory. A simple rule of thumb is derived relating the shear strength of the sediment to the pullout force. Multiple APC holes at individual sites allow the consistency of the pullout measurements to be assessed. The effects of different operational procedures during APC coring are also explored. Although generally applicable, the correlation between pullout force and laboratory measurements of shear strength breaks down for some APC holes, possibly because of the disturbance of some sediment types during the APC coring process. A better understanding of the physical process of APC coring, and its effect on the properties of the sediment both inside and immediately outside the core barrel, would indicate what confidence can be put on the measurement of pullout force as a way of evaluating the in situ shear strength of deep sea sediments.     

Interannual Sea Level Variations and Annual Tides in the Northwestern Pacific

Specific properties of the interannual sea level variations and annual tides in the Northwestern Pacific were studied. Several tide stations were monitored. The monthly mean sea level for the year of 1995 was analyzed at each tide station. A seismic event in 1995, some tectonic activity around the subject area, and the Kuroshio (the oceanic western boundary current) may possibly contaminate results which would have occurred from the astronomical annual tide alone.     

Flow Cytometric Analysis of Coastal Lagoon Bacterioplankton and Picophytoplankton: Fixation and Storage Effects

The effect of different fixation and storage protocols on the flow cytometric (FCM) simultaneous analysis of bacterioplankton and phytoplankton in coastal seawater samples (Mediterranean coastal lagoons) was investigated. FCM measurements (cell number, fluorescence and scatter characteristics) were obtained through DAPI staining. Three fixatives [glutaraldehyde (GA), formaldehyde (FA) and paraformaldehyde (PFA)] and two storage (3 months duration) methods (5 °C and −196 °C) were tested. Two dominant populations were detected in studied samples: bacteria and eukaryotic picophytoplankton. Adding fixatives (2% final concentration) appears necessary to obtain FCM exhaustive counts of all the bacteria and phytoplanktonic cells. This was related to the permeation effect of fixatives which allowed a better DAPI staining of the cells. Maximum fluorescence, i.e. optimal staining of the cells was obtained with FA or PFA, and significant lower fluorescences with GA. Fixed samples stored at 5 °C induced rapid cell loss. Only storage in liquid nitrogen of samples fixed with FA or PFA, allows mid-term (≥4 months) preservation of bacteria or picophytoplankton cell numbers, and limited evolution of DAPI-induced fluorescence and scatter characteristics.