CONCENTRATIONS AND ACTIVITIES OF IONS IN SOLUTIONS DISPLACED FROM BASALTIC SOILS

Soil solutions displaced from Antrim basaltic soils were analysed for major inorganic constituents. The solutions were nearly saturated with aluminium and phosphate but not sulphate. Iron concentrations were greatly in excess of ferric hydroxide solubility. The solutions were less concentrated than those described for soils of Britain and the U.S.A., representing a leaching environment.     

红壤对铝锰离子的吸附特征 Ⅴ.稀溶液中铝锰离子的交换吸附行为

研究了贴近自然的稀溶液条件下铝、锰离子交换吸附的行为，结果是：铝、锰与钙、钾离子的交换吸附仍符合一般的离子交换规律，但也不遵守比例定律。讨论了代入量／代出量的摩尔比〈1时的交换吸附、临界点及其机理。对k、K、1/n、r进行了表述，其中k偏高，K则偏低。从热力学角度进一步论证了红壤铝质化即酸化的自然趋势，并揭示了钙与铝、钾离子交换吸附的能量特征。     

红壤对铝、锰离子的吸附特征 Ⅰ.铝、锰离子的非等当量交换

对铝、锰离子在红壤中的吸附特征进行了研究,结果表明:离子交换能（或吸附能）的次序为铝>锰>钙>钾,但同一离子在不同固相中的交换吸附能力有异。离子的代入量和代出量随其加入量而递增,而代入量占所加数量的百分数则递减,遵守一般的离子交换规律。非等当量性为铝或锰离子参与交换所出现的一种特殊现象,是由于其水解产物的非电性吸附叠加于电性吸附所致,尤以在砖红壤体系中者为甚;非电性吸附量与平衡溶液浓度的关系符合Freundlish方程。     

THE ADSORPTION OF ALUMINIUM FROM HYDROXY-ALUMINIUM SOLUTIONS ON TO FITHIAN ILLITE

The adsorption of aluminium from hydroxy-aluminium perchlorate solutions on to Fithian illite in the presence of 0.06M and 0.5M NaClO₄ is described by Langmuir-type adsorption isotherms at constant OH/A1 ratio. The binding constant for aluminium, and the amount of aluminium that can be adsorbed, increases with increasing OH/A1 ratio of the solution from which it is adsorbed. The Langmuir-type adsorption isotherms can be explained on the basis that hydroxy-aluminium species present in solution are adsorbed in constant relative proportions and that the relative proportions of hydroxy-aluminium species remain unchanged on dilution of the hydroxy-aluminium solutions at constant ionic strength. If the ionic strength at which the isotherm is determined is decreased from 0.5M to 0.06M NaClO₄, the binding constant for adsorption of aluminium is not significantly altered. This can be understood if the adsorption process is not one of exchange but rather the formation of H bonds between the hydrolysed polymer species and the surface. Negative adsorption measurement at low and increasing ionic strength indicates the changes in charge on the adsorbed hydroxy-aluminium polymers as their concentration in solution is increased.     

红壤对铝、锰离子的吸附特征Ⅰ.铝、锰离子的非等当量交换

对铝、锰离子在红壤中的吸附特征进行了研究，结果表明：离子交换能（或吸附能）的次序为铝＞锰＞钙＞钾，但同一离子在不同固相中的交换吸附能力有异。离子的代入量和代出量随其加入量而递增，而代入量占所加数量的百分数则递减，遵守一般的离子交换规律。非等当量性为铝或锰离子参与交换所出现的一种特殊现象，是由于其水解产物的非电性吸附叠加于电性吸附所致，尤以在砖红壤体系中者为甚；非电性吸附量与平衡溶液浓度的关系符合Freundlish方程。     

红壤对铝锰离子的吸附特征 Ⅲ.铝锰离子对的交换吸附

对具有水解性质的铝、锰离子对交换吸附研究的结果是 ,两种离子既表现了离子交换的一般化学行为 ,又有明显的非等当量交换和非电性吸附的特征 ;非等当量交换和非电性吸附受制于固相的表面性质、离子对的相对交换能力和离子的加入量 ;对非电性吸附的有关参数k、K、1/n、r和ΔF进行了表述 ;根据铝离子交换锰离子的ΔF ,从热力学论证了红壤对铝离子的吸附是自发和不可逆的并趋向稳态的自然过程     

红壤对铝锰离子的吸附特征 Ⅳ.铝锰交换钙钾离子的化学现象

铝、锰离子与钙或钾质固相之间的交换吸附也出现非等当量交换和非电性吸附,而钙、钾离子对交换反应则为电性吸附;非电性吸附量决定于固相表面的场强,也与离子的水解性质和价数有关,其中以铝离子在砖红壤、红壤中的非电性吸附最为强烈;从能量角度综合说明了k、K、1/ n 与ΔF的联系,铝离子的交换吸附具有最大的k、K和最小的1/ n,ΔF为负值;从热力学进一步证论了红壤铝质化的机理,在自然条件下红壤酸化应是一个连续的自发和不可逆过程。     

EFFECT OF pH ON THE REACTION OF SODIUM FLUORIDE WITH HYDROUS OXIDES OF SILICON, ALUMINIUM, AND IRON, AND WITH POORLY ORDERED ALUMINOSILICATES

The release of hydroxyl ions from silica and ferric oxide gels on treatment with sodium fluoride solution is very small above pH values of 7.6 and 9 respectively. Hydroxyl release from alumina gel and poorly ordered aluminosilicates is appreciable at pH 9 and varies little with pH, but that from crystalline forms of alumina decreases with decrease of pH. For poorly ordered aluminosilicates, the ratio (OH′ released at pH 8.0): (OH′ released at pH 6.8) is directly proportional to the mole fraction Al/(Al+Si). The measurement of hydroxyl release at differing pH values may enable determination of hydrous alumina separately from the total poorly ordered inorganic gel material; moreover, the amount of hydroxyl released at high pH values is related to phosphate sorption capacity.     

SELECTIVE EXTRACTION OF AMORPHOUS IRON OXIDES BY EDTA FROM SOILS FROM DENMARK AND TANZANIA

Soils from Denmark and Tanzania were extracted with EDTA solutions of different concentrations and pH. After extraction for 3 months there was no significant (95% level) further increase in amounts of iron (and aluminium, calcium, and magnesium) during longer extraction periods. X-ray diffraction showed no change of the crystalline minerals caused by the extraction, which is believed to be specific for amorphous iron oxides. The EDTA method may thus serve as a reference method for the determination of amorphous iron oxides in soils. Although the difference between EDTA-extractable iron and that extracted during 2 h by ammonium oxalate at pH 3.0 in the dark may be high, the ammonium oxalate method is considered to give a fast and often fair estimate of amorphous iron oxides.     

SELECTIVE EXTRACTION OF AMORPHOUS IRON OXIDE BY EDTA FROM A MIXTURE OF AMORPHOUS IRON OXIDE, GOETHITE, AND HEMATITE

Iron (III) was extracted by EDTA and ammonium oxalate from a model substance consisting of amorphous iron oxide, goethite, and hematite precipitated in the presence of quartz sand. Even by varying the EDTA concentration between 0.02 and 0.1 M, pH between 4.40 and 6.00, the solid:solution ratio between I:25 and I:250, and using extraction times up to go days, it was found that EDTA was able to extract only a limited amount of iron. In contrast, 0.2 M ammonium oxalate at pH 3.0 is able to dissolve all the iron compounds if the extraction time is sufficient. Nevertheless, the amount of EDTA-extractable iron is equal to the amount of iron extracted after 4–5 hours with ammonium oxalateat pH 3.0. From X-ray analysis, DTA curves, a solubility product determination, and a kinetic investigation, it is concluded that the EDTA-extractable fraction consists of X-ray amorphous iron oxide, less soluble than polymeric iron hydroxide, and presumably only one compound. Therefore, it is concluded that it may be possible by means of EDTA to carry out a selective extraction of X-ray amorphous iron oxides mixed with goethite and hematite.     

A RAPID METHOD FOR DETERMINING THE SURFACE AREA OF ALUMINOSILICATES FROM THE ADSORPTION DYNAMICS OF ETHYLENE GLYCOL VAPOUR

A new method is described for determining the surface area of soils and clays by adsorbing ethylene glycol vapour under continuous evacuation at c. 10^-2 cm of mercury. The adsorption of a monolayer of ethylene glycol is inferred from the dynamics of pressure changes in the adsorption chamber. The time at which monolayer adsorption is evaluated is proportional to the total weight of ethylene glycol required to form a monolayer on all samples in the adsorption chamber. This period ranged from 30 to 75 minutes when from 0·39 to 1·56 g of glycol was adsorbed in the experiments. A single 0·75 g sample of Wyoming bentonite required 0·195 & glycol.     

COMPARISON OF AQUEOUS ACETYLACETONE AND POTASSIUM PYROPHOSPHATE SOLUTIONS FOR SELECTIVE EXTRACTION OF ORGANIC-BOUND Fe FROM SOILS

Seven samples of iron oxyhydroxides, characterised by crystallinity and surface area (monolayer water content), were examined for solubility in aqueous acetylacetone (0.68 M), potassium pyrophosphate pH 10 (0.1 M) and acid ammonium oxalate pH 3 (0.2 M). Solubilities in acetylacetone and oxalate were dependent on surface area, being 30 per cent Fe or more for non-crystalline oxides in 40 h. Solubility in pyrophosphate was 2 per cent Fe or less in 40 h even when surface area was 300 m²/g. Pyrophosphate solution was more suitable than aqueous acetylacetone for selective extraction of iron-organic complexes from soils which contain amorphous or poorly crystalline iron oxides.     

POSITIVE ADSORPTION FROM MIXTURES OF THREE ELECTROLYTE SOLUTIONS

The double layer theory was used for estimating the relative amounts of positively adsorbed cations when a mixture of three salts with mono-, di-, and trivalent cations is present in clay electrolyte systems. It is shown that the adsorbed cations are dominated by the trivalent cation when the salts are present at equal concentrations.     

THE DISTRIBUTION OF IRON, MANGANESE, AND SCOTLAND ALUMINIUM IN SOME SOILS FROM NORTH-EAST SCOTLAND

Twenty-four soils from north-east Scotland have been subjected to differential extraction techniques to determine the effect of hydromorphism on various Fe, Mn, and A1 fractions. There were pronounced losses of dithionite-extractable Fe and Mn from gleyed horizons, but the 'silicate-Fe’fraction appeared to be relatively unaffected. The oxalate-extractable Fe and A1 fractions also decreased in response to gleying. The ratio of the oxalate- to dithionite-extractable Fe fractions (Fe₀/Fe_d) increased in gleyed horizons, presumably due to variations in the rate of ageing and crystallization of amorphous Fe oxides and hydroxides.     

VERTICAL DISTRIBUTION OF EXTRACTABLE IRON AND ALUMINIUM IN SOIL PROFILES FROM A BROWN EARTH-PEATY PODZOL ASSOCIATION

Fe and Al extractable by 3 per cent oxalic acid and by 0.1M potassium pyrophosphate at pH 10 have been determined in horizon samples of two soil profiles of each of three subgroups (Brown Earth, Brown Podzolic Soil, and Peaty Podzol) developed in North Wales on parent materials derived from Silurian shales. The vertical distribution of Fe and Al together with the relationship between pyrophosphate-extractable (‘fresh’ hydrous oxides) and oxalic-extract-able Fe or Al (‘fresh’+‘aged’ hydrous oxides) can assist classification and interpretation of the course of podzolization in these soils. If podzolization is defined as sesquioxide transport, then its degree of development in the soils studied differs according to whether Al or Fe are used as the index element. The evidence supports continued recognition of soils of Brown Podzolic type as an intergrade subgroup.     

用电导热散法研究可变电荷土壤粘粒与离子的相互作用

本工作选用二种可变电荷土壤粘粒(<2μ),分别含有0.35×10^-4-1.3×10^-4mol/L的不同电解质,在不同含水量下,在5—50℃范围内测量其直流电导率的变化。试验结果表明,电导热散法是研究土壤粘粒与离子相互作用的有用手段;电导率-温度曲线上的折点温度是随含水量、电解质种类和土壤类型而不同。在相同含水量下,含有不同电解质的红壤体系的折点温度具有如下的变化顺序:CaCl₂>Na₂SO₄>KCl>Ca(NO₃)₂>NaNO₃;砖红壤体系的折点温度明显高于红壤体系。折点温度的高低是土壤粘粒与离子相互作用强度的反映。     

红壤对铝、锰离子的吸附特征Ⅱ铝、锰离子的非电性吸附

对铝、锰离子的非电性吸附进行了Freundlish方程处理 ,结果表明 :砖红壤中的吸附较红壤明显 ,低浓度时 ,锰离子的非电性吸附较铝离子为弱 ,高浓度时则反之 ;对于土壤的离子交换吸附 ,似不可能获得稳定的平衡常数k ;K表征离子的吸附强度 ,以膨润土中者最大 ,1/n是吸附量与溶液浓度的相关率 ,K和 1/n成反相关。砖红壤中的ΔGo 最大 ,铝、钾离子交换的ΔGo 大于铝、钙离子交换者。非电性吸附量及与其有关的k、K、1/n和ΔGo 既受固相表面性质的影响 ,也制约于离子的本性     

FORMATION, COMPOSITION AND STRUCTURE OF HYDROXY-ALUMINOSILICATE IONS

Formation of hydroxy-Al (HA) and hydroxy-aluminosilicate (HAS) ions was studied in solutions of A1C1₃, orthosilicic acid and NaOH. Evidence for incorporation of Si into HA is that HA retarded the development of silicomolybdate colour and Si was retained by a cation-exchanger. The reaction is believed to be mainly a condensation reaction between the hydroxyl groups in Al–OH–Al and Si–OH groups. The HAS with Si/Al ratio 0.3–0.6 showed infrared spectra similar to allophane-like constituents in Ando soils.     

REAL-TIME MEASUREMENT AND INTERPRETATION OF THE CONDUCTIVITY AND pH OF PRECIPITATION SAMPLES

A microprocessor-based acid rain monitor was used to make real-time measurements of conductivity and pH of rainwater within individual storms. The automated measurements were compared with laboratory analyses of a subset of the samples taken. The laboratory measurements tended to overestimate the pH because of temperature induced changes in dissociation and Henry's Law constants affecting ionic compounds in the rainwater. The measurement artefact due to these effects may result in average hydrogen ion concentrations being underestimated by approximately 10 to 15% at UK sites. The greatest systematic discrepancies would be anticipated at highly polluted sites and during low temperature acidic episodes. The concept of a rainwater acid fraction was investigated and found to be useful fro quality control and interpretative purposes. The field measurement of conductivity of low ionic strength samples was slightly lower than the corresponding laboratory measurement, possibly caused by limited resolutio nof the conductivity probe or dissolution of fine particulate material.