A new type of isotherm for zinc liquid-solid partitioning on δ−MnO2, γ−MnOOH and manganite in seawater

This article deals with the interaction of zinc with δ−MnO₂, γ−MnOOH and manganite existing in natural water systems. The mechanism of the reaction has been studied in detail. From the fact that the “ratio of ion exchange(%)-pH” graph is an “S shaped” curve, it is possible to deduce that the chemical reaction is of the nature of cation exchange. And since the pH range of ion exchange=4, it is possible to further deduce that the reaction can be explained by the mechanism of monovalence cation exchange. The main result of this article is the discovery of a new type of isotherm which has not been mentioned in previous literature here and abroad. This isotherm cannot be represented by any presently available adsorption isotherm equations in marine chemistry. The characteristics of this new type of isotherm are as follows: the isotherm has two “knees” and three “plateaus”, the heights of these three “plateaus” are in the ratio 1:2:3. In order to explain theoretically our new isotherm, this article suggests the application of the principle of interfacial stepwise ion exchange for liquid-solid distribution of minor elements on suspended particulate matter. The corresponding isotherm equation was derived from this theory. The results obtained in this article will be of theoretical guiding significance in the study of the marine geochemistry of zinc. Projects supported by the Science Fund of the Chinese Academy of Sciences.     

Study on the isotherms of the interaction between suspended particles and Cu (II) in the Huanghe River

The isotherms of the interaction between the suspended particles and Cu²⁺, and the effects of lysine and asparaginic acid on the isotherms in the Huanghe (Yellow) River were studied by applying the theory and method of interfacial stepwise ion/coordination particle exchange. We obtained a new stepped river isotherm, formed by two curves joined together with a “plateau” in the middle. The adsorption equilibrium constantsK ₁ andK ₂ were calculated by using the isothermal equation of surface stepwise ion exchange. Amino acid in small amount promotes exchange adsorption of the suspended particles with Cu²⁺. The degree of promotive action relates to the isoelectric point of amino acid. The promotive effect of lysine is bigger than that of asparaginic acid. Project 29361001 supported by NSFC.     

Effect of organics (fulvic acid and amino acids) on the interaction between Cu(II) and clays in sea water II. Isotherms and isotherm equations

In the present paper, determination of isotherms of the exchange reaction between Cu(II) and clays is presented, verifying again the “cation exchange—surface precipitation” isotherm worked out formerly in our laboratory. A modified BET equation was applied to treating the experimental data and describing the new isotherm. In addition, the mechanism of the effects of organics are further discussed and verified. Based on the isotherm equations and the estimates of the average area occupied by a single molecule on the surface, we put forward a new hypothesis which differs from the current one of “organic film”. Projects sponsored by the Science Fund of the Chinese Academy of Sciences.     

Plateau typeE(%)- pH curves of interfacial exchange between liquid and solid in seawater

A study on the curves of the exchange ratioE(%)- pH on the liquid-solid interface of the systems Zn (II) with clay minerals, (Kaolinite, illite and montmorillonite), Zn (II) with hydrous ferric oxides (amorphous ferric oxide, geothite and hematite), Zn (II) with hydrous manganese oxide (γ-MnOOH, manganite and δ-MnO₂) etc. in seawater resulted in the discovery of new plateau type exchange ratioE(%)-pH curves not yet reported in literature. The two factors that decide the growth, decline and the change of the “plateau type” curve are: (1) the inherent characteristics of systems, which can be explained by the exchange constants (i=1, 2, 3, etc.) of interfacial stepwise ion/coordination particle exchange between liquid and solid; and (2) . The theory of interfacial stepwise ion/coordination particle exchange in seawater was applied to explain the experimental results of the above study and a general formula was derived for the plateau type exchange ratioE(%)-pH curves. The theoretically simulated and calculated curves coincided well with the experimental results. This paper provides new and powerful experimental basis to support the theory of interfacial stepwise ion/coordination particle exchange in seawater. The project was supported by the National Natural Science Foundation of China.     

The effect of amino acids on copper (II)-goethite ion exchange in seawater

In seawater, aside from metal elements and suspended particles, organic substances amount to about 500–2,000 ug carbon/l^[8], which is not neglegible in comparison with that of minor metal elements. But in the study of the interaction of the three constituents (metal elements, organics, and suspended particles), the effect of organics in seawater on the surface reaction of metal element—suspended particles has usually been neglected. Recent theoretical research^{[1, 11]} confirmed the importance of the effect of organics in seawater on the surface reaction of metal element—suspended particles. Generally, the effect of organics on the reaction of metal ions, especially Cu(II), on a solid surface is either promotive^[2] or inhibitive^{[7, 9]}. So far the fact that organics cannot affect the surface reaction of Cu(II) ions on solids has not been reported in literature. Our experimental results showed that none of the amino acids in seawater affect Cu(II)-goethite ion exchange under certain experimental condition (such as amino acid of lower concentration and lower pH). It was known that the metal ion-organics complex in a liquid competing with solids for metal ions may inhibit the surface reaction of metal ions on solids, but the mechanism of the complex reaction of metal ions competing with solids is not known yet. In fact, the decrease of surface site-exchanging due to the surface reaction of organics on solids is also inhibitive. It is also explained by the ion exchange isotherm of the “amino acid-Cu(II)-geothite” system. This result further demonstrates that the theory of interfacial stepwise ion exchange is applicable to the metal ion exchange isotherm with the presence of organic substances in the system. Projects supported by the Science Fund of the Chinese Academy of Sciences     

PLATEAU TYPE E(%)-pH CURVES OF INTERFACIAL EXCHANGE BETWEEN LIQUID AND SOLID IN SEAWATER

A study on the curves of the exchange ratio E(%)-pH on the liquid-solid interface of the systems Zn(II) with clay minerals (Kaolinite , illite and montmorillonite), Zn(II) with hydrous ferric oxides (amorphous ferric oxide, goethite and hematite). Zn(II) with hydrous manganese oxide (y-MnOOH, manganite and 5-MnO2) etc . in seawater resulted in the discovery of new plateau type exchange ratio ?%)-pH curves not yet reported in literature. The two factors that decide the growth , decline and the change of the " plateau type " curve are : (1) the inherent characteristics of systems , which can be explained by the exchange constants i(i=1 ,2 , 3 . etc .) of interfacial stepwise ion / coordination particle exchange between liquid and solid ; and (2)The theory of interfacial stepwise ion/coordination(the amount of solid exchange reagent)particle exchange in seawater was applied to explain the experimental results of the above study and a general formula was derived for the plateau type exchange ratio E(%)-pH c     

STUDY ON THE ISOTHERMS OF THE INTERACTION BETWEEN SUSPENDED PARTICLES AND Cu (Ⅱ) IN THE HUANGHE RIVER

ＩＮＴＲＯＤＵＣＴＩＯＮＴｈｅｖａｒｉｏｕｓｐｈｙｓｉｃａｌａｎｄｃｈｅｍｉｃａｌｒｅａｃｔｉｏｎｓｔｈａｔｏｃｃｕｒｂｅｔｗｅｅｎｔｈｅｓｕｓｐｅｎｄｅｄｐａｒｔｉｃｌｅｓ,ｓｅｄｉｍｅｎｔｓ,ｅｔｃ.ａｎｄｈｅａｖｙｍｅｔａｌｓｉｎａｎａｔｕｒａｌａｑｕａｔｉｃｓｙｓｔｅｍｐｌａｙｅｘｔｒｅｍｅｌｙｉｍｐｏｒｔａｎｔｐａｒｔｓｉｎｃｏｎｔｒｏｌｌｉｎｇｔｈｅｄｉｓｔｒｉｂｕｔｉｏｎｐａｔｔｅｒｎ,ｍｉｇｒａｔｉｏｎａｎｄｔｒａｎｓｆｏｒｍａｔｉｏｎｏｆｈｅａｖｙｍｅｔａｌｓｔｈｅｒｅ.Ｓｉｎｃｅ…     

Fourier-transform infrared spectroscopic studies on the interaction among marine trace metal ions,solid particles and organics

IR spectra of Cu (II)-marine solid particle systems show that Cu(II)-marine solid particle ion exchange causes a stepwise change in the surface H-bonding hydroxyl groups on illite, montmorillonite, CaCO₃, γ-AlOOH and goethite, but that this does not affect the surface free hydroxyl groups on illite, montmorillonite and CaCO₃, and framework hydroxyl group on goethite and on γ-AlOOH. Over the range of Cu (II) exchange amounts in the present experiment, four stepwise changes were discovered for the surface H-bonding hydroxyl group on illite, while two stepwise changes were observed on the other marine solids. The interfacial stepwise ion exchange theory was first demonstrated by the above experimental evidence.     

Evaluation of coal bed methane content using BET adsorption isotherm equation

Coal bed methane is unconventional raw natural gas stored in coal seam with considerable reserves in China.In recent years,as the coal bed methane production,the safety and the use of resources have been paid more attentions.Evaluating coal bed methane content is an urgent problem.A BET adsorption isotherm equation is used to process the experimental data.The various parameters of BET equation under different temperatures are obtained;a theoretical gas content correction factor is proposed,and an evaluation method of actual coal bed methane is established.     

Effects of Fe and Mn on the growth of a red tide dinoflagellateScrippsiella trochoidea (Stein) Loeblch III

Batch culture experiments were conducted with a red tide dinoflagellateScrippsiella trochoidea (Stein) Loeblch III collected from Jiaozhou Bay, Shangdong, China. Growth rates and oellular Chl—a were measured in media with iron and manganese ion concentrations controlled at different levels using EdTA-trace metal buffer systems. Cell density increased 3.2 times to 6.5 times over the range of lowest (0 mol/L) to highest (10⁻⁵ mol/L) iron and manganese ion concentrations. The range of cell density response was much lower than the range of total available iron and manganese, which was >100—fold that of Fe. This nonlinear relationship indicates that the cells adapt to make more efficient use of iron and manganese under limiting conditions. The cellular Chl—a content maximized after 3 days incubation and then decreased gradually under either iron or manganese limitation conditions. It indicated that the algae gained higher photosynthesis ability when transferred to a new environment. Growth responses to iron and manganese limitation can be both modeled according to the equation of Monod. The half—saturation constant for growth,k, is 4.6×10⁻⁸ mol/L for Fe and 5.1×10⁻⁸ mol/L for Mn. Our results showed that the iron availability in Jiaozhou Bay does not limit the growth ofS. trochoidea. Contribution No. 2831 from the Institute of Oceanology, Chinese Academy of Sciences. Project 9389008 supported by NSFC; Study supported by PDB6.     

The surface reaction on liquid-solid interface of “amino acid-Cu(II)−MnO2” system in seawater

The results obtained from the Cu(II)%-pH curve of the system in the presence of added amino acid indicated that the added amino acids of higher concentration can inhibit the Cu(II)-σ-MnO₂ ion exchange and that their inhibiting effects decrease in the following sequence when the initial amino acid concentrations are 20.00 ppm: histidine > cystine > glutamic acid > proline > alanine > glycine. The determination of amino acid in solution performed with an amino acid analyser showed that added amino acids react chemically on the surface of the σ-MnO₂ According to thermodynamic equilibria relations in the system, amino acids can be changed to amines because of their decarboxylation on the surface of the σ-MnO₂. Considering (1) the effect-inhibiting factor of amine F_A(β, K_a, pH) representing the complex potential of amine with Cu(II) in solution and (2) the acidic constant of −NH ₃ ⁺ group in the amine molecule representing the ability of cation exchange of the amine with σ-MnO₂, the inhibiting seqence of added amino acid of 20.00 ppm (Eq.(1)) is reasonable. Thus added amino acids do inhibit Cu(II)-σ-MnO₂ ion exchange because (1) the amino acid and/ or amine, which is the decarboxylate of the corresponding amino acid, complex with Cu(II) in solution and compete with σ-MnO₂ for Cu(II); (2) the cation exchange of the amino acid and/or amine reduce the exchange site on the surface of the σ-MnO₂. The results obtained from the isotherms indicated that the theory of interfacial stepwise ion exchange can be extended to the Cu(II) σ-MnO₂ ion exchange system in the presence of added amino acid.     

考虑吸附相体积的页岩气储量计算方法

页岩气赋存于发育大量天然微裂缝的页岩中,主要以吸附态和游离态2种形式存在。准确评价裂缝中自由气量对于页岩气井开采的早期评价具有明显的实用价值。从物质平衡原理出发,运用Langmuir吸附模型、Bangham固体变形理论,同时考虑基质孔隙体积和裂缝孔隙体积随地层压力的变化,以及吸附气所占体积对储量的影响,推导出了修正吸附相所占体积的页岩气藏物质平衡方程,并给出了线性化方法。计算结果表明,考虑了吸附气所占孔隙体积后,基质中自由气量比不考虑吸附相体积时减小,且吸附气量减小,裂缝中自由气量相对增加,总储量减小,使得计算模型更符合实际,计算结果更为准确。      

Effects of composition and structure of alginates on adsorption of divalent metals

Results of a series of experiments (on the adsorption of divalent metal ions by dried alginic acid, Na and Ca alginates of different composition and block structure) conducted in this systematic study of the effects of the composition and structure of alginates on the static adsorption equilibrium of divalent metal ions indicate that the properties of alginate adsorption to divalent metal ions are highly different, depending not only on the cations used, but also on the form and structure of the alginates. There is close correlation between the adsorption properties and the structure of the alginates. The selectivity coefficient of Na alginate for Cd-Sr ion exchange tends to increase with the increase of theM/G ratio in alginate, whereas the adsorption capacity of Ca alginate for Cu²⁺ ion decrease with the increase of the G-block or the average length of the G-block and the total adsorption capacity of alginic acid is found to vary in the same order as theF _MM(diad frequency) in alginate in the mixed solution of Sr²⁺, Ba²⁺ and Cd²⁺. Contribution No. 2166 from the Institute of Oceanology, Chinese Academy of Sciences.     

Transfeer of organic pollutants during sewage-seawater mixing

The transfer processes of organic pollutants during sewage-seawater mixing were simulated in three different mixing systems. The release rate of organic matter from sewage particles to seawater was found to be about 0.02–0.04 d⁻¹. The release processes can be simulated by an exchange-equilibrium kinetic model. Degradation of COD was observed in all three mixing systems and can be described by a first order kinetic equation. The degradation rate constantk ranged between 0.04 and 0.07 d⁻¹. These results have provided important parameters for estimation of environmental capacity.     

Effect of bis(tributyltin) oxide on reproduction and population growth rate of calanoid copepod Schmackeria poplesia

A full life-cycle toxicity test, combined with histology, on calanoid copepod Schmackeria poplesia was used to study the effect of bis(tributyltin) oxide (TBTO). The results indicate no sex-specific differences in TBTO toxicity. Long-term mortalities of the copepods exposed to concentrations higher than 20 ng TBTO L⁻¹ were significantly elevated compared with that of control, and larval development was inhibited when they were exposed to 40 and 60 ng TBTO L⁻¹. The percentages of ovigerous females were reduced compared with the control (P<0.01) after 24 days exposure to concentrations higher than 10 ng TBTO L⁻¹. Histological examinations suggest that exposure to TBTO might block the posterior end of the diverticula and inhibits the production of egg sacs. A modified Euler-Lotka equation was used to calculate a population-level endpoint, the intrinsic rate of natural increase (r _m), from individual life-table endpoints, i.e. mortality rate, time of release of first brood, sex ratio, the fraction of ovigerous females among all females as well as the number of nauplii per ovigerous female. Apart from the highest TBTO concentration (60 ng L⁻¹), where all females aborted their egg sacs, 20 ng TBTO L⁻¹ was the only concentration that significantly decreased r _m compared with that of control (an effect associated with decreased sex ratio). The results show that the S. poplesia is affected by prolonged exposure to low concentrations of TBTO. The full life-cycle toxicity test combined with histology experiments provides more integral understanding of the toxicity of endocrine disrupters.     

The preparation and antioxidant activity of glucosamine sulfate

Glucosamine sulfate was prepared from glucosamine hydrochloride that was produced by acidic hydrolysis of chitin by ion-exchange method. Optical rotation and elemental analysis characterized the degree of its purity. In addition, the antioxidant potency of chitosan derivative-glucosamine sulfate was investigated in various established in vitro systems, such as superoxide (O-2)/hydroxyl (·OH) radicals scavenging, reducing power, iron ion chelating. The following results are obtained: first, glucosamine sulfa...     

Dietary manganese requirement ofP. Vannamei

Graded levels of manganese were supplemented to a semi-purified diet containing 45% crude protein, to provide six levels of manganese (i. e. containing 5, 25, 50, 70, 140 and 210×10⁻⁶, respectively) for two experiments with these experimental diets. The initial weight of shrimp used in the 35–day experiment I was 0.30±0.04 g, and that in the 70–day Experiment II was more than one gram. The results showed that optimum content in the semi-purified diet for the more than 1 gram shrimp ranged from 70 ×10⁻⁶, to 140×10⁻⁶, but supplementation of Mn was not necessary for the small shrimp. Contribution No. 2673 from the Institute of Oceanology, Chinese Academy of Sciences.     

The intrinsic acidity constants and specific surface area of marine solid particles

This paper deals with the infrared spectra of “amino acid-clay, calcium carbonate and γ-AlOOH” and “Cu(II)-clay-amino acid” model systems, and shows that the model of the ternary surface complex is M-OHLCu (L=amino acid) for marine solid particle-Cu (II)-amino acid. Study of the formation mechanism of the ternary surface complex shows that the specific surface area, and especially the intrinsic acidity constant, determine whether the ternary surface complex is easily formed, and that factor,F _TSC, quantifies the relationship between the promoting effect of organics on M_t-marine solid particle ion exchange and the intrinsic acidity constant and specific surface area.     

Physical and interfacial chemistry of Huanghe estuary

Summarized results of studies on the physical and interfacial chemistry of the Huanghe estuary are presented as follows: 1. The relationship between the exchange ratio (%) and pH for the Cu (II)-Sedi.ments of the Huanghe Estuary and that of the Cu (II)-illite system were observed to be very similar. 2. A stepwise ion/coordination particle exchange isotherm of trace metal in Huanghe estuary sediment was derived. 3. The ion/coordination particle exchange between trace metal and Huanghe Estuary sediment is analogous to the interfacial chemical characteristic of illite.     

Study on gametophyte vegetative growth ofUndaria pinnatifida and its applications

When cultured under certain environmental conditions (25°C, light intensity 80 μmol/m²·s, LD 12/12, in enriched seawater medium with 7×10⁻⁴ mol/L NO₃−N, 1.56×10⁻⁴ mol/L, PO₄−P and supplements of other elements like Mn, Fe, I, etc.), male and female gametophytes ofU. pinnatifida kept growing vegetatively and propagated fast at average daily fresh weight increase rate of about 20%. The empirical formulaG _m=G _o·3^m was established to estimate the output of vegetative gametophytes. Vigorous vegetative gametophyte cells began to form reproductive structures (oogonium and spermatangium, when the temperature was lower than 25°C and other environmental factors were kept optimal. The sufficient supply of gametophyte cells provided enough seeds for raisingUndaria sporelings on production scale. Controlled cross-breeding experiments using selected male and female gametophyte clones which increase their cell number by mitosis instead of meiosis were also carried out in vitro. Juvenile sporophytes from the cross-breeding had almost the same length and width increase rates as those of the control. The fact that vegetative gametophytes can be purposely selected, propagated quickly, cross-bred, with the resulting sporophytes having almost the same characteristics leads to a new way to select desiredUndaria strains for long time use without losing the desired economic characteristics. Contribution No. 2696 from the Institute of Oceanology, Chinese Academy of Sciences. Supported by National Natural Science Foundation of China.