电解质浓度对土壤吸附铜离子时氢离子释放的影响

研究了不同铜离子浓度、不同电解质浓度情况下,吸附铜离子时氢离子释放对两种可变电荷土壤和4种恒电荷土壤悬液pH的影响。研究结果表明,除了黄棕壤外,含铁量越高,由于吸附铜离子后所引起的土壤ΔpH最大值越小。加入的铜离子浓度为10-4molL-1时,铜离子吸附对中和曲线形状没有根本影响。在较低浓度时,铜离子吸附时氢离子的释放较少;而在较高浓度时,当体系pH值大于一临界值时,开始释放大量氢离子。氧化铁是引起恒电荷土壤和可变电荷土壤在吸附铜离子时氢离子释放差异产生的主要原因。电解质浓度的变化对恒电荷土壤和可变电荷土壤吸附铜离子后中和曲线变化影响有很大的区别,含铁量越高,电解质浓度对土壤吸附铜离子后的氢离子释放的影响越小。     

可变电荷土壤吸附铜离子时氢离子的释放

可变电荷土壤吸附铜离子后 ,土壤的中和曲线上不出现pH突跃 ,而变成一条平缓变化的曲线。当土壤悬液的pH低于一定数值时 ,加入铜离子后不释放氢离子。该pH值与土壤中氧化铁的含量有关。氧化铁的含量越高 ,该pH值越高。对于大多数可变电荷土壤 ,此pH值为 4左右。对可变电荷土壤 ,pH值越接近 4,氢离子释放的快速过程越不明显。在pH 4左右 ,加入铜离子后 1 0分钟时 ,释放的氢离子量仅占 6 5分钟时释放量的 3 0 %左右。但当pH值高于 4 5时 ,在大多数情况下 ,加入铜离子后半分钟时释放的氢离子量即可占 6 5分钟时的 5 0 %以上。恒电荷土壤吸附铜离子时氢离子的释放速度比可变电荷土壤快得多。即使pH值低至 3 8,在加入铜离子后半分钟时氢离子的释放量即占 6 5分钟时的 5 6 %以上。可变电荷土壤吸附铜离子时的H/Cu比比恒电荷土壤大得多。当恒电荷土壤悬液中加入0 1mo1L- 1 NaNO3作支持电解质时 ,吸附铜离子时的H/Cu比增大。     

可变电荷土壤中铜离子的解吸

研究了我国四种可变电荷土壤红壤、赤红壤、砖红壤和铁质砖红壤以及二种恒电荷土壤黄棕壤和黑土中吸附性铜离子的解吸特征。研究结果表明 ,可变电荷土壤吸附的一部分铜离子可以被去离子水解吸 ,而且在pH～解吸率曲线上在一定pH值时出现解吸率最大值。在最大值时不同土壤中铜离子解吸率的大小与土壤中氧化铁的含量有关。氧化铁的含量越高 ,在最大值时铜离子的解吸率越大。当用中性电解质解吸可变电荷土壤吸附的铜离子时 ,电解质的浓度越大 ,解吸率越低。与此相反 ,恒电荷土壤吸附的铜离子不能被去离子水解吸 ,只能被中性电解质解吸 ,且电解质的浓度越高 ,解吸率越大。这表明 ,可变电荷土壤中吸附性铜离子的解吸规律 ,完全不同于恒电荷土壤中者。本文初步讨论了其原因     

离子强度和pH对可变电荷土壤与铜离子相互作用的影响

研究了离子强度和pH对可变电荷土壤表面电荷与铜离子吸附的影响。作为对照 ,也研究了它们对恒电荷土壤黄棕壤的有关性质的影响。结果表明 ,随pH升高 ,土壤的表面负电荷增加 ,正电荷减少。对于可变电荷土壤 ,可出现电荷零点 (pH0 )。随pH升高 ,土壤对Cu2 的吸附量增大。随着离子强度增大 ,恒电荷土壤对Cu2 的吸附百分率明显降低 ,可变电荷土壤对Cu2 离子的吸附百分率也降低 ,但降低的幅度比恒电荷土壤者小得多。土壤中氧化铁的含量越高 ,降低的幅度越小。对于含 2 1 %左右游离氧化铁的铁质砖红壤 ,即使支持电解质NaNO3的浓度高达 1molL- 1,对Cu2 的吸附仍然几乎没有影响。从离子强度和pH与土壤表面电荷和铜离子吸附的关系 ,可以推测在土壤对铜离子的吸附中 ,既存在电性吸附 ,又存在专性吸附。在可变电荷土壤对铜离子的吸附中 ,专性吸附较为重要     

茶多酚和铜对可变电荷土壤钙镁释放的影响

通过批平衡试验,研究茶多酚、铜和体系pH对可变电荷土壤释放钙镁离子的影响。研究发现,铜离子初始浓度为2.0mmol/L,最终体系pH为5.0时,随着茶多酚添加量的增加,可变电荷土壤表面的负电荷增加,土壤表面释放的钙镁离子量减少。茶多酚初始添加量为20 g/kg,最终体系pH为5.0时,随着铜离子初始浓度的升高,可变电荷土壤对铜离子的吸附量增加,铜离子通过与钙镁离子发生离子交换,形成对吸附位点的竞争,从而增加钙镁离子的释放。茶多酚初始添加量为20 g/kg,铜离子浓度为2.0 mmol/L,随着pH的升高,可变电荷土壤钙镁离子释放量下降。在相同pH条件下,茶多酚可以通过自身的吸附增加可变电荷土壤表面负电荷,减少可变电荷土壤钙镁离子的释放量。研究结果可为茶园土壤酸化和污染控制提供参考。     

不同浓度铜离子土壤的吸附-解吸行为——兼论弱专性吸附态的存在

研究了三种可变电荷土壤和两种恒电荷土壤不同铜离子浓度条件下的吸附-解吸行为。结果表明,不同铜离子浓度下土壤的pH-Cu2+吸附率曲线均在低pH段出现会合,且随着铜离子浓度升高,pH-Cu2+吸附率曲线有向右偏移的趋势。证实了可变电荷土壤中吸附性铜离子可被去离子水解吸,并存在解吸峰现象。针对解吸前后吸附体系pH值的变化研究结果显示,吸附时体系pH低于5.0时,解吸后pH上升;而吸附体系pH高于5.0时,解吸后pH下降,表明pH5.0可能是土壤吸附铜离子机理发生变化的又一个转折点。本文还对专性吸附中弱吸附态的存在和形成原因进行了初步探讨。     

恒电荷土壤及可变电荷土壤与离子间相互作用的研究Ⅲ Cu2+和Zn2+的吸附特征

研究了3种典型可变电荷土壤和4种典型恒电荷土壤在不同pH和不同浓度下单纯及共存体系中Cu2 和Zn2 的吸附及其影响因素。结果表明,两类土壤对Cu2 或Zn2 的吸附量均随平衡浓度增加而增大,符合Langmuir吸附等温式;当Cu2 、Zn2 浓度一定时,pH升高使Cu2 、Zn2 吸附量增大,但当pH >5时,Cu2 、Zn2 吸附量随pH变化甚微,出现一个接近最大吸附量的“平台”。当添加Cu2 、Zn2 浓度相同,但二种离子的总浓度不同时,平衡液的Cu2 /Zn2 浓度比均小于1,说明两类土壤对Cu2 的吸附选择性大于Zn2 ,且这种趋势不因pH和离子浓度而改变。当Cu2 、Zn2 共存时,使可变电荷土壤的Zn2 吸附量减小约70 % ,是恒电荷土壤降低量的约1.5倍;可变电荷土壤吸附一个Cu2 或Zn2 时所释放H 的平均数,明显大于恒电荷土壤者,说明可变电荷土壤对Cu2 及Zn2 的吸附中专性吸附的比例较恒电荷土壤大     

离子强度对可变电荷表面吸附性铜离子解吸的影响:高岭石

为了解连续性解吸对可变电荷表面吸附性铜离子解吸的影响,研究了高岭石在去离子水和0.1 mol L~(-1) NaNO_3溶液中吸附铜离子后,依次在去离子水以及浓度由低到高的NaNO_3溶液中连续解吸时,离子强度变化对不同pH段铜离子解吸的影响。结果表明:在去离子水中和不同浓度NaNO_3中解吸吸附性铜离子时,pH-解吸分值曲线的变化趋势完全不同。在去离子水中解吸时可出现重吸附现象,而在NaNO_3中解吸时出现解吸峰现象。高岭石pH-铜离子解吸分值曲线的拐点pH与pH吸附有着对应关系,且pH特征与高岭石pH0关系密切。离子强度变化导致的吸附表面电位变化、高岭石边面的诱导水解作用和土壤表面电荷性质随pH升高的变化被认为是导致这些现象的原因。     

离子强度对可变电荷表面吸附性铜离子解吸的影响:可变电荷土壤

为进一步了解离子强度对可变电荷表面吸附性铜离子连续性解吸的影响,研究两种可变电荷土壤在去离子水和0.1 mol·L~(-1)NaNO_3溶液中吸附铜离子后,依次在去离子水和浓度由低到高的NaNO_3溶液中连续解吸时,离子强度变化对不同pH段铜离子解吸的影响。结果表明,解吸过程中离子强度变化方向对解吸分值随pH升高的变化趋势的影响完全不同,当离子强度由大变小时,解吸分值曲线的总体趋势是随着pH的升高而降低,反之,曲线呈现为钟形,且当去离子水第一次解吸在0.1mol·L~(-1)NaNO_3溶液中吸附的铜离子时,两种可变电荷土壤的第一次去离子水解吸均可出现重吸附现象,但铁质砖红壤解吸分值绝对值要小于红壤。整个解吸过程中,两种可变电荷土壤的铜离子吸附性铜离子的解吸特征与高岭石基本相似,但可变电荷土壤与高岭石以及两种可变电荷土壤之间,解吸分值的变化规律均存在一定的差异性,可变电荷土壤中的氧化铁含量多少被认为是导致这些差异的主要原因。     

恒电荷土壤及可变电荷土壤与离子间相互作用的研究 Ⅱ.共存体系中Cl-的吸附特性

对 3种可变电荷土壤和 4种恒电荷土壤在陪伴阳离子分别为Na 、K 、NH 4 、Mg2 、Ba2 、Al3 和共存SO2 -4下Cl- 的吸附量进行了测定。结果表明 ,供试土壤的Cl-吸附量顺序均为AlCl3>BaCl2 和MgCl2 >KCl和NH4 Cl>NaCl,其中可变电荷土壤的差异较大。不同电解质溶液中Cl- 吸附量的顺序与土壤所带正电荷量的顺序一致。Langmuir方程的K值较小 ,且在不同介质中的差异不大。随SO2 -4浓度的增大 ,可变电荷土壤对Cl- 的吸附量减少 ,平衡液的pH值增大 ,而恒电荷土壤则变化甚微 ,说明共存的SO2 -4使可变电荷土壤的表面负电荷增加 ,但对恒电荷土壤则影响不大。这些结果说明 ,Cl- 以电性吸附的机理不因介质而变。可变电荷土壤在一价阳离子存在时 ,除土壤本身所带的正电荷外 ,还有一价阳离子吸附后产生的正电荷以及由此引起的对Cl- 的协同吸附。在二、三价阳离子存在时 ,还有Cl- 的离子对吸附 ,而恒电荷土壤在所有介质中 ,似乎总是以与Cl- 的协同吸附为主     

Specific and non-specific adsorption of inorganic ions

The authors reported that the relative bonding strength between ligand of soil colloid surface and cations could be obtained easily by the measurement of MCSA, and that the MCSA corresponded to the constant of Langmuir's adsorption isotherm equation.

The relative bonding strength of cations with respect to kaolinitic soil clay at pH 6 was, Cr³⁺>Fe³⁺, Al³⁺>Ga⁸⁺>Cu⁸⁺>Pb²⁺>Y³⁺, La³⁺>Mn²⁺>Ni²⁺, Co²⁺> Zn²⁺>Sr²⁺, Mg²⁺>NH⁴⁺, K⁺, and with respect to colloid with humus coating, Y³⁺, La³⁺>Pb²⁺>Cu²⁺, and the other orders were same.

The solubility of cations in soil colloid aqueous dispersion system was calculated from the values of MCSAs, and considered as follows, Y³⁺, La³⁺, Cu³⁺, Pb³⁺, Mn²⁺, Ni²⁺, CO²⁺: concentration in soil solution and soil geochemical mobility may be regulated by the specific adsorption reaction, Zn²⁺, Mg²⁺, Sr²⁺, K⁺, NH⁴⁺: concentration in soil solution and soil geochemical mobility may be regulated by the non-specific adsorption reaction, but at neutral to alkaline condition, Zn²⁺ and Mg²⁺ may specifically adsorb on soil, clays, Fe³⁺, Cr³⁺, Al³⁺, Ga³⁺: concentration in soil solution and soil geochemical mobility may be regulated by the solubility of their oxide hydrates.     

Reactions of fulvic acid with metal ions

Fulvic acid is a water-soluble humic material that occurs widely in soils and waters and that tends to form water-soluble and water-insoluble complexes with a variety of metal ions, some of which are toxic. This paper presents information on the conditions under which the different types of FA-metal complexes are formed. The solubility in water, separately and after mixing, of FA (2 to 30 mg/100 ml) and eleven metal ions (Fe(III), Al, Cr(III), Pb, Cu, Hg(II), Zn, Ni, Co, Cd and Mn; 1 × 10^?5 moles of each metal ion) was investigated over the pH range 4 to 9. After mixing, the solubility of the components was significantly affected by pH only when less than 20 mg of FA was present. As the systems became richer in FA (22 to 30 mg), most of the metal ions remained in the aqueous phase, likely due to the formation of FA-metal complexes, inhibiting the formation of metal hydroxides. The order in which the eleven metal ions tended to form water-insoluble FA-metal complexes depended on the pH. At pH 6 it was: Fe = Cr = Al > Pb = Cu > Hg > Zn = Ni = Co = Cd = Mn. This order appeared to correlate with the valence, 1st hydrolysis constants and effective hydrated ionic diameters of the metal ions. In general, FA/metals weight ratios of > 2 favored the formation of water-soluble FA-metal complexes; at lower ratios, water-insoluble complexes, which could accumulate in soils and sediments, were formed.     

Activation of soil pyrophosphatase by metal ions

Inorganic pyrophosphatase activity in three soils decreased when exchangeable and soluble metals were removed by leaching with in NH₄OAc (pH 8). The effect of added metal ions at various concentrations in the leached soils showed that, at certain concentrations, Ba²⁺, Ca²⁺, Co²⁺, Mg²⁺, Mn²⁺, Ni²⁺ and Zn²⁺ promoted, K⁺ and Na⁺ had no effect, and Fc²⁺ and Cu²⁺ decreased pyrophosphatase activity. At high concentrations (>50 mM). Co²⁺, Mn²⁺, Ni²⁺ and Zn²⁺ inhibited pyrophosphatase activity in two soils. The concentration of metal ion needed for optimum activity of pyrophosphatase varied among the soils. The efficiency of the metal ions at optimum concentrations (average percentage increase for three soils in parentheses) in promoting pyrophosphatase was Ca²⁺ (47) > Mg²⁺ (42) > Ba²⁺ = Co²⁺ (29) > Ni²⁺ (27) > Zn²⁺ (20) > Mn²⁺(16). Pyrophosphatase activity in two leached soils adjusted to 50, 75, 100 or 150 mM PPi and Ca²⁺ or Mg²⁺ concentrations from 0 to 250 mM was at an optimum when the metal ion: PPi ratio was 1:1. Soil pyrophosphatase in the presence of 200 mM CaCl₂ or MgCl₂ was protected against inactivation by heat (90 C for up to 30 min).     

施用碱稳定污泥污水土壤经γ-辐照后土壤溶液中Cu和Zn

Soil samples collected from several acid soils in Guangdong, Fujian, Zhejiang and Anhui provinces of the southern China were employed to characterize the chemical species of aluminumions in the soils. The proportion of monomeric inorganic Al to total Al in soil solution was in the range of 19% to 70%, that of monomeric organic Al (Al-OM) to total Al ranged from 7.7% to 69%, and that of the acid-soluble Al to total Al was generally smaller and was lower than 20% in most of the acid soils studied. The Al-OM concentration in soil solution was positively correlated with the content of dissolved organic carbon (DOC) and also affected by the concentration of Al³⁺. The complexes of aluminum with fluoride (Al-F) were the predominant forms of inorganic Al, and the proportion of Al-F complexes to total inorganic Al increased with pH. Under strongly acid condition, Al³⁺ was also a major form of inorganic Al, and the proportion of Al³⁺ to total inorganic Al decreased with increasing pH. The proportions of Al-OH and Al-SO₄ complexes to total inorganic Al were small and were not larger than 10% in the most acid soils. The concentration of inorganic Al in solution depended largely on pH and the concentration of total F in soil solution. The concentrat ions of Al-OM, Al³⁺, Al-F and Al-OH complexes in topsoil were higher than those in subsoil and decreased with the increase in soil depth. The chemical species of aluminumions were influenced by pH. The concentrations of Al-OM, Al³⁺, Al-F complexes and Al-OH complexes decreased with the increase in pH.     

Extraction of heavy metal ions sorbed on clays

The ability of seventeen different chemical solutions to displace heavy metal ions (Pb, Zn, Cu, Cd), pre-adsorbed on clay (kaolinite, illite and montmorillonite) at either pH 5 or 7, has been examined and the relative efficiency of each extractant ascertained. Of the reagents used, only EDTA (0.001 M, pH 7) quantitatively released all four ions from the three clays; oxalic acid (0.1 M, pH 3.3), totally displaced at least three ions from each clay. Other reagents, for example ammonium oxalate (0.1 M), ammonium nitrate (0.01 M), nitric acid (0.1 M) and sodium citrate (0.01 M) effectively displaced one or more heavy metal ions from individual clays. Near quantitative displacement by an excess of Na (0.1 M) or Ca (0.05 M) ions was observed only on montmorillonite. Pre-adsorption at pH 7 was accompanied by precipitation of excess metal ion, and the extraction efficiency in these systems was determined by the ability of the reagent to both dissolve hydrous oxide species and displace sorbed metal ions. The implications of the results with respect to the nature of the adsorption process and relevance to environmental systems have been considered.     

Genetically encoded sensors for ions and metabolites

Many of the genes encoding important trans porters and metabolic enzymes have been identified over the last ten years. Moreover it has been possible to study the biochemical properties of the corresponding proteins in great detail. It is expected that by 2,010 biochemical functions will have been assigned to many of the products of the approximately 30,000 Arabidopsis genes. We will get closer to understanding the biological function of the gene products by systematic analysis of mutants using knock-out and TILLING approaches. Metabolomics initiatives complement these approaches by providing insight into the changes in cellular ion and metabolite profiles in the mutants, thus giving information essential for the construction of cellular and whole plant models. However, one important dataset especially relevant to multicellular organisms is lacking: the knowledge of the spatial and temporal profiles of ions and metabolite levels at cellular and subcell ular levels. To address this issue, we have developed protein-based nanosensors for several metabolites, providing a set of tools for the determination of cytosolic and subcellular ion (e.g. iron and zinc) and metabolite levels in real time using fluorescence-based microscopy. The prototypes of these sensors were shown to function in vitro and also in vivo, i.e. in yeast and in mammalian cell cultures. One future goal is to expand the set of sensors to a wider spectrum of targets by using the natural spectrum of periplasmic binding proteins from bacteria and by computational design of proteins with altered binding pockets. Application of nanosensor technology to plant cells and tissues will help to elucidate the special and temporal distribution of ions and metabolites.     

Evaporation of impurity ions from solutions into the air

A mechanism is proposed for low-temperature transfer of impurity ions from electrolyte solutions into air taking into account the physico-chemical structure of the liquid and its surface, as well as meteorological factors. The model adequately describes the experimental data obtained by the present authors, and Azad and Latham (1967). The recommendations on concentration limits for some industrial impurities in sewage are given.     

Role of phosphate and carboxylate ions in maillard browning

The Maillard reaction of carbohydrates and amino acids is the underlying chemical basis for flavor and color formation in many processed foods. Phosphate and other polyatomic anions will accelerate the rate of Maillard browning, and this effect has been explained by invoking enhanced proton abstraction from intermediate Amadori compounds. In this work, the effect of phosphate and carboxylate ions on browning was measured for a series of reducing sugars with and without the presence of beta-alanine. Significant browning was observed for sugars alone suggesting that polyatomic anions contribute to Maillard browning by providing reactive intermediates directly from sugars. A mechanism is proposed for decomposition of sugars by polyatomic anions and efforts to trap reactive species using o-phenylenediamine (OPD) are described. The results of this study suggest how complications may arise from the popular usage of phosphate buffers in the study of Maillard reaction kinetics. In addition, the results imply how phosphates may be useful for enhancing browning during food processing.