Effective diffusion coefficient of cations as influenced by physical and chemical properties of selected Indiana soils

Abstract

Ion diffusion through the soil matrix is dependent upon both the physical and chemical properties of the soil. Cation (K, Na, Ca and Mg) diffusion coefficients De, were determined for seven Indiana soils by using the ion diffuison flux to a hydrogen resin paper technique. Volumetric moisture, clay content exchange and solution phase ionic concentrations, buffer capacity and organic C content were variously related to the determined De values. The larger the diffusion coefficient of K, Ca, and Mg, the lower the clay content, and exchange capacity of soils, and the higher the concentration of these cations in the solution phase. From the present study, it was concluded that the De of these cations was affected by one or more soil physical and chemical property which must be considered if De is to be used to estimate supply rate of these ions to growing roots in soil systems.     

Ionic equilibria,selectivity and diffusion of cations in soil as influenced by anion additions

Abstract

An experiment was carried under controlled conditions to investigate the influence of the anions, H₂PO₄ ^‐. and Cl on the ionic equilibria, selectivity and effective diffusion of Rb, K, Na, Ca, Mg in two Indiana soils.

Additon of anions to the soils increased the concentration of cations in soil solution. In both the soils receiving H₂PO₄ ^‐, lower cation concentrations were found in the soil solution than in those receiving Cl^‐ . Additon of H₂PO₄ ^‐and Cl^‐ reduced the ion selectivity coefficient, k, for various homovalent (Rb/K, Rb/Na, K/Na, Ca/Mg) and mono‐divalent ion pairs (Rb/Ca, Rb/Mg, K/Ca, K/Mg). In Zanesville soil treatments receiving H₂PO₄ ^‐ had lower k values for mono‐divalent cations than treatments receiving Cl^‐. However, no such conclusions could be drawn for Raub soil. Soils treated with H₂PO₄ ^‐ had higher k values for homovalent cations than Cl^‐ treated soils. The differences in the selectivity of adsorption in these two soils might be attributable to the differences in the type and nature of exchange materials and cation concentrations on the exchange phase.

Addition of H₂PO₄ ^‐ or Cl^‐ enhanced the magnitude of effective diffusion coefficient. (De) of all the cations under considerations. The magnitude of effective diffusion coefficient for cations was lower for H₂PO₄ ^‐ treated soils than Cl^‐ treated soils. Such a reduction in De is related to the reduction in cation concentration in soil solution thereby increasing the buffer capacity for the ions under consideration.     

ION EXCHANGE IN SOILS FROM THE ION PAIRS K–Ca,K–Rb,AND K–Na1

Isotopic exchange of ⁴³K, ²⁴Na, ⁸⁶Rb, and ⁴⁵Ca was used to measure the equilibria between some arable soils and mixed chloride solutions of the ion pairs, K–Ca, K–Rb, and K–Na; the results were interpreted by a thermodynamic treatment of the exchange isotherm (Gaines and Thomas, 1953). The cation exchange capacities of the soils were not constant for the three ion pairs and decreased appreciably with K-saturation in the K–Ca systems because Ca ions were trapped inside the interlayer spaces. That soils preferred K to Na in the K–Na systems and Rb to K in the K–Rb systems, was explained in terms of the standard free-energy changes of the exchange reactions. The activity coefficients of the adsorbed ions, f, changed with K-saturation differently for the three ion pairs: fNa and fCa decreased continuously with increasing K-saturation whereas fRb remained almost constant. However, with increasing K-saturation, fK increased in the K–Na systems, remained unchanged in the K–Rb systems, and first increased and then decreased in the K–Ca systems. These changes are interpreted in terms of the effect of the various ions on the interlayer space of 2 : 1 type clay minerals and the possible distribution of adsorbed ions between the Gouy and Stern layers.     

Study on the Threshold Values of Soil Potassium Parameters for Release and Fixation: A Prognostic Approach to Improve the Use Efficiency of Soil and Fertilizer Potassium

The reserve of nonexchangeable potassium (K), threshold levels for release and fixation of intermediate K, and the Gapon exchange selectivity coefficient for K to calcium (Ca) and magnesium (Mg) exchange were studied in soils of widely varying properties, with a view to optimize the efficiency of native as well as added fertilizer K for plant uptake. The illite-dominated soils recorded greater reserve of nonexchangeable K and showed greater cumulative K release. The threshold values of soil K parameters for release and fixation of intermediate K were found to vary with the change in background electrolyte concentration. The soils dominated by illite were found to possess greater K threshold release and fixation values. In general, the fixation threshold level was greater than release threshold level. The Gapon exchange selectivity coefficient for K to Ca exchange revealed that K ions were more tightly held in the specific sites than in planar sites.     

磷钾肥施用对日光温室土壤溶液离子组成的影响

采用土培模拟试验研究了施用磷、钾肥对大田和温室土壤溶液电导率（EC）、离子含量及其比例的影响。结果表明,温室栽培土壤溶液EC、K+、Na+、Ca2+、Mg2+、NO3-含量以及K+ / Ca2+、K+ / Mg2+摩尔比分别为大田土壤的2.5、95.0、16.6、1.9、3.2、4.0、31.0和39.0倍,说明日光温室土壤离子累积及养分比例失调问题突出。施用磷、钾肥对土壤溶液中不同离子含量的影响不同,增加磷肥施用量,显著降低了大田和温室土壤溶液EC和Ca2+、Mg2+离子含量,而对土壤溶液K+、NO3--N和NH4+-N离子浓度均无显著影响;随施钾量增加,大田及温室土壤溶液EC、K+、Na+、Ca2+、Mg2+和K+/Ca2+、K+/Mg2+摩尔比均呈显著增加趋势。温室栽培实践中因过量施用磷、钾肥而造成的阳离子养分比例失调而带来的营养及生态环境问题值得关注。     

Ion adsorption mechanisms in oxidic soils; implications for point of zero charge determinations

In order to clarify the adsorption mechanisms for various ions (e.g., P, K, Ca, Mg), ion adsorption studies were carried out on a range of soils of widely different mineralogical compositions. The soils were classified as: Hydrandept, Gibbsihumox, Eutrustox and Haplustoll and belonged, respectively, to the Honokaa, Halii, Wahiawa and Waialua soil series in Hawaii.Soils containing mostly hydrous Fe and Al oxides, thus colloids of the variable-charge type, retain ions through various types of adsorption mechanisms. As a result, certain interactions between cation adsorption and anion adsorption occur which affect the ion exchange processes and thereby the determination of the point of zero charge (PZC).In this study adsorbed phosphate increased the adsorption of cations and lowered the PZC and adsorbed Ca interfered with PZC determinations unless these were carried out with CaCl₂ as supporting electrolyte. It is likely that this latter interference will have influenced the results of many earlier studies because of the very strong adsorption of Ca by oxidic colloids. In this study only part of the adsorbed Ca could be recovered from the two most highly weathered soils, by repeated extractions with NH₄-acetate at pH 7.The results indicate that many soils of the tropics can be characterized effectively by their PZC's. One should be aware, however, of the effects of strongly adsorbed ions commonly present in these soils and thus use those supporting electrolytes for the PZC determinations which counteract these effects.     

REACTIONS OF AMMONIA WITH SOIL. I

Heats of adsorption and adsorption isotherms of ammonia gas were measured at 300 K (27 °C) on outgassed soil saturated with Na⁺, K⁺, NH₄⁺, Ca²⁺, or Mg²⁺ ions. The Ca and Mg soils adsorbed apparently one more NH₂ molecule per exchangeable ion than the Na and K soils, mostly in the relative pressure range o to 0.005, but not much more than the NH₄ soil. The initial heat of adsorption was c. 75 kJ mol^-1 on the Ca and Mg soils and c. 60 kJ mol^-1 on the other soils. The results suggest that most NH, is sorbed on these soils through reactions not involving exchangeable cations.     

伊朗西部地区碱性土壤中共离子对Zn吸附的影响

Zinc(Zn) is essential to plant growth and relatively mobile in soils.This study was conducted to assess the effect of common ions(Ca 2+,K +,Na +,NH + 4,Cl,NO 3,and H 2 PO 4) on sorption of Zn in surface samples of ten calcareous soils from western Iran using 10 mmol L 1 KCl,KNO 3,KH 2 PO 4,Ca(NO 3) 2,NaNO 3,and NH 4 NO 3 solutions as background electrolytes.The results indicated that both NH + 4,K +,and Ca 2+ equally decreased Zn sorption as compared to Na +.Zinc sorption was decreased by H 2 PO 4 as compared to NO 3 and Cl.The Langmuir and Freundlich equations fitted closely to the sorption data of all ions.The Langmuir maximum,bonding energy constant,and Freundlich distribution coefficient for Zn sorption differed among the various ionic background electrolytes.Langmuir sorption parameters showed that the presence of H 2 PO 4 decreased the maximum Zn adsorbed,but increased the bonding energy.Although K + and NH + 4 equally influenced maximum Zn adsorbed,they differed in their effect on the distribution coefficient of Zn in soils.Values of saturation index calculated using Visual MINTEQ indicated that at the low Zn concentration,Zn solubility was controlled by sorption reactions and at the high Zn concentration,it was mainly controlled by sorption and mineral precipitation reactions,such as precipitation of Zn 3(PO 4) 2.4H 2 O,Zn 5(OH) 6(CO 3) 2,and ZnCO 3.For most ionic background electrolytes,soil pH,CaCO 3,and cation exchange capacity(CEC) were significantly correlated with sorption parameters.     

Relationship between water soluble and exchangeable soil cations for estimating plant uptake and leaching potential

Abstract

The relationship between water soluble and exchangeable cations (Ca, Mg, Na, and K) was investigated for surface horizons of 195 soils including many taxonomic categories and a wide range in physical and chemical properties from around the world. This will provide information on exchangeable soil cation solubility for use in estimating plant uptake and leaching potential. Amounts of water soluble and exchangeable cations were not consistently related (r² of 0.50, 0.08, 0.77, and 0.49 for Ca, Mg, Na, and K). High correlations were biased by high water soluble and exchangeable cation levels of a few soils that had 3.8‐ and 2.5‐fold greater mean than median values. The ratio of exchangeable to water soluble cations was closely related to cation saturation (r² of 0.87, 0.95, 0.95, and 0.93 for Ca, Mg, Na, and K, respectively). As the degree of saturation of the exchange complex by a certain cation increased, solubility Increased. A change in saturation had less effect on K than on Na, Mg, and Ca solubility. Only exchangeable soil cations (NH₄OAc extractable) are routinely measured and reported in soil survey reports, thus, water soluble levels may be determined from cation saturation. This will allow estimation of the amounts of cation that can potentially move in solution through the soil or be taken up by plants. Use of cation saturation, in addition to exchangeable content, will better characterize soil cation availability by representing quantity, intensity, and buffer factors.     

The Impact of Road De-Icing Salts (NaCl) on Colloid Dispersion and Base Cation Pools in Roadside Soils

The maintenance of safe-drivingconditions in snow and ice-affected areas in thewintertime includes the use of sodium chloride (NaCl)as de-icing salts. In this study, the impact of NaClon soil-colloid mobilisation and exchangeablebase-cation leaching has been evaluated. The chemistryof groundwater samples below an infiltration trenchfor highway runoff and leachate from column studiessuggested that soil-colloid mobilisation had occurred,as the exchangeable sodium (Na) concentration and theelectrical conductivity (EC) in the groundwater/columnleachate reached the threshold values for colloiddispersion. Generally, samples with no dispersionproblems had high Na and calcium (Ca) concentrations,suggesting that the initial effect of the de-icingsalt was to stabilise the colloids. In the columnstudy there was a good agreement between the degree ofcolloid dipersion problems and lead (Pb) concentrationwhen the pH value was above 7.0. Significant negativecorrelations between Na/CEC (cation exchange capacity)and Ca/CEC in roadside soils from three sitesindicated that Na preferentially displaces Ca from theexchange sites. However, the groundwater dataindicated that Na ions also displace potassium (K) andmagnesium (Mg). A positive effect of NaCl seen at onesite was an increase in the K concentration, which ishighly likely an effect of Na ions displacing fixed Kbetween the layers of 2:1 type clay minerals. In soilslacking these types of clay minerals, severe Kshortage may result from a high plant demand combinedwith the low K concentration in the readily availablefractions in the original soil and a highsusceptibility to leaching. The most significantimpact on soil exchange processes was found to occurwithin 6 m from the road.     

恒电荷土壤及可变电荷土壤与离子间相互作用的研究 I.共存离子对NO_3~-吸附的影响

研究了我国典型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Ｋ十、Ｎａ十、Ｃａ２＋时和１ｍｍｏｌＬ－１ＫＣ１、Ｋ２ＳＯ４支持电解质中ＮＯ３－的吸附。结果表明，ＮＯ３－吸附量随ｐＨ的增加而减小。在添加相同浓度ＮＯ３－时，３种可变电荷土壤对ＮＯ３－的吸附量顺序为Ｃａ（ＮＯ３）２＞ ＫＮＯ３＞ＮａＮＯ３＞ＫＮＯ３十ＫＣＩ＞ＫＮＯ３＋Ｋ２ＳＯ４；在初始ＮＯ３－浓度０．５－５ｍｍｏｌＬ－１的范围内，吸附量随浓度变化的关系符合Ｌａｎｇｍｕｉｒ等温吸附式．由此求出与ＮＯ３－吸附结合能有关的常数（Ｋ）在不同共存离子存在下数值较小且差异不大，因此认为不同陪伴阳离子和不同伴随阴离子对ＮＯ３－吸附的电性机理影响不大，只是改变了土壤表面的正电荷数量从而使吸附量发生变化。４种恒电荷土壤对ＮＯ３－的吸附量通常很小，其中在Ｃａ（ＮＯ３）２介质中较在其他介质中稍大，最大吸附量仅为１．５～ｍｍｏｌ ｋｇ－１左右，约为可变电荷土壤的１／１０，且在浓度较低时常观察到负吸附。     

Calcium nutrition of the sugarbeet

Abstract

When sugarbeet seedlings are transferred from a complete nutrient solution to one from which Ca has been withheld, the rootlets and tops fail to develop. The same transfer at the eight‐leaf stage causes the rootlets to become stubby and swollen at the tips and blade expansion becomes modified; particularly the upper portions of the blades attaining nearly full development, which pucker and often develop a cupping or hooding effect; a unique symptom characteristic of Ca deficiency. As each new leaf develops, the blade area becomes smaller until only a black tip remains at the apex of the petiole, which is the symptom referred to as tip‐burn for this petiole and the successively . shorter petioles formed as Ca deficiency increases in severity. Strangely, these symptoms also appear during periods of rapid growth when the nutrient solution contains as much as 10 to 28 milliequivalents per liter of Ca or when soils are high in Ca. This implies that Ca absorption and possibly translocation limits the Ca supply at the growing point. Increasing Mg in the nutrient solution decreases Ca uptake and increases Ca deficiency. Potassium deficiency, unexpectedly, induces Ca deficiency apparently by decreasing the translocation of Ca to the growing point.

These phenomena suggest the hypothesis that when ion absorption takes place from the root exchange site that has the affinity for H > Ca > Mg > K > Na, then the H generated internally replaces, and the roots absorb, Na, K and Mg preferentially. Externally, Ca would be adsorbed preferentially from the nutrient solution by the exchange complex, and with the addition of Mg, it would compete for the common adsorption site of Ca and limit Ca absorption internally. Under these conditions potassium‐deficient nutrient solutions would not induce Ca deficiency by decreasing Ca absorption but rather by decreasing Ca translocation. Theoretically, Ba would replace H more readily than Ca on the exchange complex, and therefore, Ba would be adsorbed preferentially and Ca uptake would increase. This effect of Ba was verified experimentally.

Since the translocation of ⁴⁵Ca to the growing point was found to be unrestricted under Ca‐sufficient and Ca‐deficient conditions and since the formation of insoluble Ca compounds such as phosphate or oxalate did not account for the Ca deficiency at the growing point, the cause of the Ca deficiency at the growing point is most likely the higher priority of the storage root for Ca over tops when leaf blades and storage root are both expanding rapidly. However, Ca retransport from older to younger parts of the sugarbeet plant may be restricted by the formation of Ca phosphate under Ca‐deficient conditions and Ca oxalate under Ca‐sufficient conditions.

Calcium deficiency increases net photosynthesis per unit blade area initially, probably because of blade puckering, but not on a per unit chlorophyll basis.     

The importance of exchangeable cations and resin-sink characteristics in the release of soil phosphorus

The significance of exchangeable cations in the release of phosphorus by sequential extraction with water was evaluated in 11 acid (_pH 5.0–6.3) New Zealand soils contrasting in P status and P retention. The release of P from Na-saturated soil exceeded that from the original Ca-dominated soils by up to four-fold. Possible explanations for the larger P release in the Na system include: (i) desorption of P induced by increased surface negative potential associated with the exchange of Na for Ca/Mg, and/or (ii) accelerated dissolution of Ca phosphate compounds or complexes resulting from the creation of a sink for Ca.
The potential of a series of anion- and cation-exchange resin systems (AER and CER, respectively) as sinks for labile soil P was also examined. For all soils studied, P extracted by AER-HCO₃ 3 and that removed by sequential extraction with water. Also, the amounts of P extracted by AER-OH/CER-H and NaCl/ H₂O were closely correlated ( r = 0.95**), suggesting similar release mechanisms. The results obtained indicate that charge-balancing cations, particularly Ca which is the predominant exchangeable cation in the majority of soils, exerts a more significant control on soil P equilibria in acid soils than is commonly recognized.     

Base cation-enhancing role of corn straw biochar in an acidic soil

Biochar affects base cation retention and leaching when it is used to enhance the base cation status of acidic soil. However, the details of its contribution are not yet clear. In this study, six loadings of corn straw biochar (0%, 2%, 4%, 6%, 8% and 10%, w/w) were applied to an acidic Ferralsol and incubated for 1 year. The results showed that the content of water-soluble and exchangeable base cations of K, Na, Ca and Mg increased with increasing levels of biochar in amended soil. The percentage of water-soluble Na, Ca and Mg of amended soil significantly decreased, while the percentage of exchangeable K, Ca and Mg increased significantly after the addition of biochar. For K and Na, biochar affected their leaching concentrations both as a source and by increasing the pH. For Ca, biochar reduced Ca leaching when the biochar loading was ≥4%, and the contribution increased from 30.8% to 100% at 4%–10% loading. For Mg, biochar reduced Mg leaching at biochar loadings 2%–10%, the reduction increasing from 22.0% to 70.5%. The results show that corn straw biochar can increase the content of the soil nutrient base cations K, Ca and Mg by increasing their exchangeable forms and enhance soil retention by decreasing their leaching. Thus, corn straw biochar can be used to effectively improve acidic soil base cation fertility.     

Magnesium accumulation and mineral balance in sudangrass as influenced by potassium,calcium and sodium

Abstract

Sudangrass (Sorghum sudanense, ‘Piper’ Stapf) was grown in the greenhouse in a slightly calcareous sample of Shano silt loam. The purpose of the study was to evaluate plant response to Mg and to determine any changes in Mg nutrition following individual or composite application of Mg, Ca, K and Na as nitrate compounds. The concentration of Mg in plant tissue decreased following K application and increased with each increment of Mg applied irrespective of variations in the proportions of Ca and Na included in the treatments. A base treatment including Ca, Na, and K applied with or without Mg showed a significant yield response to Mg. The Mg response was attributed to a more favorable ionic balance in the growth medium with respect to Mg because the soil was not particularly Mg deficient. Application of Mg in this case lowered the plant K concentration significantly, increased the concentration of Mg, and gave a lower K/(Ca+Mg) ratio in the foliage than was obtained without Mg. Results suggest that high levels of other nutrient cations may adversely affect the Mg nutrition of crops growing on alkaline soils not abundantly supplied with available Mg.     

The effect of Ca and K levels on the herbage yield and nutrient composition of barley plants grown in high Mg soils

Abstract

The effects of Ca and K levels on barley (cv. Johnston) yield were studied in soil media containing high levels of Mg. The dry matter yield of barley decreased with increasing concentrations of Mg in soils, but the decrease was small. Dry matter yield was positively related to concentration of K in the soil. However, additions of fertilizer Ca or K did not increase dry matter yield, indicating that depressed yield associated with high Mg levels was not due to reduced availability of Ca or K. In commercial agriculture, applications of either Ca or K to such soils are unlikely to prove beneficial in increasing crop yields.

Concentrations of Mg in soil solutions of unfertilized soils were lower than levels which were previously shown to reduce crop yield. Additions of N fertilizer increased Mg concentrations to levels which could reduce barley yield     

Application of High Copper and Zinc Compost and Its Effects on Soil Properties and Growth of Barley

Abstract

A compost of high copper (Cu) and zinc (Zn) content was added to soil, and the growth of barley (Hordeum vulgare L.) was evaluated. Four treatments were established, based on the addition of increasing quantities of compost (0, 2, 5, and 10% w/w). Germination, plant growth, biomass production, and element [nitrogen (N), phosphorus (P), potassium (K), calcium (Ca), sodium (Na), magnesium (Mg), iron (Fe), Cu, manganese (Mn), and Zn] contents of soil and barley were determined following a 16‐week growing period. Following harvesting of the barley, analysis of the different mixtures of soil and compost was performed. Micronutrient contents in soils as affected by compost additions were determined with diethylene–triamine–pentaacetic acid (DTPA) (Cu, Mn, Fe, and Zn) or ammonium acetate [Ca, Na, Mg, K, cation exchange capacity (CEC)] extractions, and soils levels were compared to plant uptake where appropriate. Increasing rates of compost had no affect on Ca, Mg, or K concentration in barley. Levels of Cu, Zn, Mn, and Na, however, increased with compost application. High correlations were found for DTPA‐extractable Cu and Zn with barley head and shoot content and for Mn‐DTPA and shoot Mn content. Ammonium acetate–extractable Na was highly correlated with Na content in the shoot. High levels of electrical conductivity (EC), Cu, Zn, and Na may limit utilization of the compost.     

The spatial heterogeneity of chemical properties in acid forest soils and its importance for tree nutrition

For two sites in the Black Forest, presence, extent and ecological significance of structure-dependent chemical. heterogeneity in the rhizosphere of acid forest soils is discussed. The heterogeneity is demonstrated by two independent methods. First, by comparison of soil solution composition in (quasi-) equilibrium with undisturbed soil cores and sieved soil samples. Water soluble K, Ca and Mg show a selective depletion on aggregate surfaces. Second, by comparison of cumulated amounts of exchangeable ions obtained from percolated homogenized soil samples and undisturbed soil cores. The release of exchangeable K, Ca and Mg is less, if soil structure is not destroyed. The finding that aggregate surfaces are more depleted of exchangeable and water-soluble K, Ca and Mg is common in aggregated acid forest soils. As aggregate surfaces bind soil water with low suction, that is where the roots preferentially grow. Consequently, a considerable underestimation of chemical stress in the rhizosphere is possible, if soil structure is destroyed for analysis.     

日光温室栽培对土壤养分累积及交换性养分含量和比例的影响

研究了日光温室栽培下陕西关中地区不同土壤养分累积及交换性养分含量及比例的变化,结果表明：日光温室栽培下土壤有机质、硝态氮、有效磷和速效钾等养分显著累积,土壤阳离子交换量明显增加,而土壤pH却出现下降趋势。日光温室土壤交换性K^＋含量显著增加;日光温室和大田土壤交换性Ca^2＋含量相比无明显差异,而日光温室土壤交换性Mg^2＋的含量及其离子饱和度有所提高。日光温室土壤钙饱和度、Ca/K和M g/K均明显低于大田土壤。认为日光温室栽培下大量施用钾肥,是土壤钙离子饱和度及Ca/K和M g/K比例降低的主要原因,建议在评价日光温室土壤养分有效性时,应综合考虑交换性养分的含量、饱和度及离子间的比例关系。     

DISPLACEMENT OF AMMONIUM IONS FOR CATION EXCHANGE CAPACITY MEASUREMENTS

The best reagent for displacing adsorbed NH, for the measurement of cation exchange capacity of soils is a mixed ZN nitrate solution of potassium and calcium. The equivalent ratio of K to Ca should be in the range from 1 to 3. This mixture is better than simple solutions of Li, Na, K, Mg, Ca, Sr, and Ba nitrates and mixtures of KNO₃ with any one or two of these other nitrates.