Improved thermodynamic calculations for concentrated mixed electrolyte systems including ion pairing (or the absence of it)

Knowledge of the activity coefficients of solutes under temperature and pressure ranges of interest is generally required for calculations of the physicochemical properties of aqueous multicomponent electrolyte solutions such as seawater. Whilst these activity coefficients are well characterized for the predominant salts individually, fewer data are available for minor components under a sufficiently wide range of conditions and there are significant interactions between some of the chemical species involved which can substantially alter the required activity coefficients in mixtures.For these reasons, accurate thermodynamic predictions for seawater and other multi-electrolyte solutions in moderate or high concentration are more difficult than is often supposed. In particular, progress in this area has been slowed by uncertainty regarding the nature and extent of ion pairing in concentrated strong electrolyte solutions, a problem that has been debated for decades. Zdanovskii's rule, described originally almost a century ago but widely neglected, provides a fundamentally sound method for calculating the properties of mixed electrolyte solutions. Modelling developments are described, which accord with various types of experiment, from our laboratory and from the chemical literature. It has become clear that, when treated in an appropriate way based on solvent activity, linear mixing behaviour of strong electrolyte solutions can be considered the norm. This is an inevitable consequence, first recognized by Guggenheim, of the cancellation of ion pairing and other interactions as, conceptually, one ion replaces another. Stronger solute–solute interactions, described by equilibrium constants, can then easily be coupled in a thermodynamically consistent manner.     

各种类型河蟹育苗用水的水质分析

近几年,河蟹人工育苗已成为我省沿海种苗培育单位的重要产业 ,随着育苗规模的不断扩大及所带来的可观经济效益,各地又因地制宜发展起地下海水、浓缩海水的育苗生产,为搞清这几种育苗水体的水质特点 ,作者对这几种水体进行了分析检测,以服务于生产 ,为河蟹育苗的健康发展提供科学依据。１工作内容和方法１．１采样点自然海水采于营口市老边区三道沟和盘锦市二界沟;浓缩海水采于营口市青石岭育苗室及营口盐 　种型苗水ｐ ＣＤ营盐含量Ｔａｂ .1　ｐＨ ,ＣＯＤａｎｄｎｕｔｒｉｔｉｏｎｓａｌｔｏｆｅｖｅｒｙｋｉｎｄｏｆｂｒｅｅｄｉｎｇｗａ…     

连续流动分析法测定污水中阴离子表面活性剂、总氮、总磷、挥发酚、氰化物、硫化物的方法及实例

快速同时测定排污口样品中阴离子表面活性剂、总氮、总磷、挥发酚、氰化物、硫化物的分析方法。采用连续流动分析法,确定最佳实验方案。经多次试验验证,呈良好线性关系;质量控制样品测定值均在保证值范围内,样品回收率在95．2％～104％之间,RSD小于2％。     

Determination of Free Nickel Ion Concentrations Using the Ion Exchange Technique: Application to Aqueous Mining and Municipal Effluents

Free metal ion concentration is generally considered a useful indicator of a metal’s bioavailability and ecotoxicity to aquatic biota. This article reports the speciation of nickel in mining and municipal effluents from Sudbury (Ontario, Canada), and also in model solutions containing a fully characterized laurentian fulvic acid (LFA) at environmentally relevant concentrations. A column ion exchange technique (IET) using a cation exchange resin (Dowex 50W-X8) was applied to determine free nickel ion concentrations. In model solutions, reasonable correlation was found between the predictions of an equilibrium-based computer speciation code, Windermere Humic Aqueous Model (WHAM) VI, and the results obtained by IET at low nickel-to-fulvic acid ratios. However at higher mole ratios, the WHAM VI predicted higher free nickel ion concentrations than IET. Only three out of six effluent samples showed reasonable agreement between the IET and the WHAM VI results, indicating the need for further development of IET for application to effluent waters.     

赤道附近局地激发LS-TAD的事例观测

大尺度行进式大气扰动(LS-TAD)通常被认为起源于极区高纬,本文报道了一起激发于低纬赤道地区、在北半球向高纬传播的LS-TAD观测事例.2002年8月10日07:30 UT,CHAMP卫星在30°W磁赤道附近观测到显著的大气密度增强,在随后的2个连续轨道上,该密度增强依次出现在北半球更高纬度上,表现出明显的极向位移,...     

Saturn's magnetospheric interaction with Titan as defined by Cassini encounters T9 and T18: New results

We present new results of Cassini's T9 flyby with complementary observations from T18. Based on Cassini plasma spectrometer (CAPS) and Cassini magnetometer (MAG), compositional evidence shows the upstream flow for both T9 and T18 appears composed of light ions (H⁺ and H₂⁺), with external pressures ∼30 times lower than that for the earlier TA flyby where heavy ions dominated the magnetospheric plasma. When describing the plasma heating and sputtering of Titan's atmosphere, T9 and T18 can be considered interactions of low magnetospheric energy input. On the other hand, T5, when heavy ion fluxes are observed to be higher than typical (i.e., TA), represents the limiting case of high magnetospheric energy input to Titan's upper atmosphere. Anisotropy estimates of the upstream flow are 1<T_⊥/T_‖<3 and the flow is perpendicular to B, indicative of local picked up ions from Titan's H and H₂ coronae extending to Titan's Hill sphere radius. Beyond this distance the corona forms a neutral torus that surrounds Saturn. The T9 flyby unexpectedly resulted in observation of two “wake” crossings referred to as Events 1 and 2. Event 2 was evidently caused by draped magnetosphere field lines, which are scavenging pickup ions from Titan's induced magnetopause boundary with outward flux ∼2×10⁶ ions/cm²/s. The composition of this out flow is dominated by H₂⁺ and H⁺ ions. Ionospheric flow away from Titan with ion flux ∼7×10⁶ ion/cm²/s is observed for Event 1. In between Events 1 and 2 are high energy field aligned flows of magnetosphere protons that may have been accelerated by the convective electric field across Titan's topside ionosphere. T18 observations are much closer to Titan than T9, allowing one to probe this type of interaction down to altitudes ∼950 km. Comparisons with previously reported hybrid simulations are made.     

Oxygen isotopic distribution along the otolith growth axis by secondary ion mass spectrometry: Applications for studying ontogenetic change in the depth inhabited by deep-sea fishes

This study using tuna otoliths as working standards established a high lateral resolution and precision analysis to measure δ¹⁸O_otolith by secondary ion mass spectrometry. This analytical approach of the ion probe was applied to deep-sea fishes to reconstruct the likely depths inhabited by the fishes at different life history stages based on the measured δ¹⁸O_otolith values as a proxy of water temperature. Dramatic increases up to 5–6‰ in δ¹⁸O_otolith, representing a temperature decrease of approximately 20 °C, were detected in a blind cusk eel (Barathronus maculatus) otolith and in the otoliths of Synaphobranchus kaupii during leptocephalus metamorphosis to glass eel, inferred from the drop of otolith Sr/Ca ratios and increase of otolith growth increment width. δ¹⁸O_otolith profiles clearly divided the fish's life history into a planktonic stage in the mixed layer of the ocean and a benthic stage on the deep-sea ocean bottom. The habitat shift signal was recorded within a 150 µm width of otolith growth zone, which was too narrow to be clearly detected by mechanical drilling and conventional isotopic ratio mass spectrometry. However, variations down to −7‰ were found in δ¹⁸O_otolith profiles as the result of Cs²⁺ beam sputter in the core and larval portions of the otoliths. Carbon mapping by electron probe microanalyzer and staining by toluidine blue suggested abundant proteins existed in the areas with anomaly negative δ¹⁸O_otolith values, which cannot be interpreted as a habitat change but due to the isotopic fractionation by O emission from the proteins. These results implied that careful design and understanding of the chemical composition of the analytical areas or tracks on the heterogeneous otolith was essential for highly accurate and precise analysis.     

Preconcentration of trace multi-elements in water samples using Dowex 50W-x8 and Chelex-100 resins prior to their determination using inductively coupled plasma atomic emission spectrometry (ICP-OES)

This work presents a solid phase extraction (SPE) method for simultaneous preconcentration of trace elements in water samples prior to their ICP-OES determination. Dowex 50W-x8 and Chelex-100 resins were used as SPE sorbent materials for preconcentration of trace Cd, Co, Cr, Cu, Fe, Ni, Pb and Zn. The optimum sample pH, eluent concentration and sample flow rates were found to 6, 3.0 mol L⁻¹ and 3.0 mL min⁻¹, respectively. In terms of multi-element preconcentration capabilities, Dowex 50W-x8 appeared to be a better sorbent. The recoveries for all the tested analytes were >95%. However, Chelex-100 showed a better performance in terms of recovery (>95%) towards Cu, Fe and Zn. Under optimized conditions using Dowex 50W-x8, the relative standard deviations for different metals were <3%. The limits of detection and limits of quantification ranged from 0.01–0.39 μg L⁻¹ and 0.05–0.1.3 μg L⁻¹, respectively. The accuracy of the preconcentration method was confirmed by spike recovery test and the analysis of certified reference materials. The SPE method was applied for preconcentration of the analyte ions in tap water, bottled water and wastewater samples.     

A comparison between manganese nodules and cobalt crust economics in a scenario of mutual exclusivity

The past 20 years have been characterised by limited interest in the economic viability of deep seabed mining with the exception of those mineral ores rich in precious metals such as polymetallic sulphides. This paper goes against the tide. After reviewing the most significant literature, it compares the economic feasibility of mining polymetallic manganese nodules and cobalt-rich ferromanganese crusts in a scenario of mutual exclusivity. It uses a new indicator, the cobalt-nickel price ratio, whose aim is to verify at what metal prices the net present value of the two mining projects equalises. Previous research has shown that the turning margin between manganese nodules and cobalt crusts is a cobalt price of $50/kg. The present paper revises this by showing that the choice between mining crust and nodules depends on fluctuations in the price of nickel. A Monte Carlo simulation proves that cobalt crust mining could be reasonably preferred to manganese nodules at cobalt prices of $40-60/kg if the price of nickel fell below $11/kg. Within this condition, investors would receive the minimum acceptable internal rate of return of 15%, which is at a level of risk closer to the land-based mining. However, when the price of nickel passes the $11/kg threshold, the equilibrium between the two ventures can be reached only at a cobalt price greater than $100/kg, causing cobalt crust to become uncompetitive. Finally, the paper, recognising that prices are not unique drivers, introduces legal, political, technological and environmental concerns to show that the final choice between the two mining ventures cannot be merely driven by economic issues.     

Recovery of Plant Nutrients from Dilute Solutions of Human Urine and Preliminary Investigations on Pot Trials

Within the context of Ecological Sanitation (ECOSAN), human urine has been the subject of research and practice as a potential fertilizer in the recent years. Although quite a lot had been done with original undiluted urine with promising outcomes, not much appears in the literature which concentrates on dilute solutions of urine. This is important because unless waterless toilets are employed, urine will be diluted with flush water in actual use. In this work, dilute solutions of urine are investigated with emphasis on the recovery of plant nutrients. A natural zeolite namely clinoptilolite was loaded with nitrogen, phosphorus, and potassium as an indirect route of processing urine. The results have revealed that hydrolysis is completed in shorter times in dilute samples. Clinoptilolite could successfully remove plant nutrients from all dilute solutions. Nitrogen could be recovered up to 86% with higher efficiencies at higher concentrations in general. Recovery of orthophosphates increases with increasing concentration to reach 96%, however, potassium could not be recovered. The preliminary experiments with grass have revealed that nutrient loaded clinoptilolite was as effective as chemical fertilizers while direct application of original and diluted solutions of urine had shown inferior yields.