Adsorption and Desorption of Boron as Influenced by Soil Properties in Temperate Soils of Lesser Himalayas

Boron (B) adsorption increased with increasing concentration. Langmuir adsorption isotherm was curvilinear. The maximum value of adsorption maxima (b1) was observed Sagipora soil and maximum bonding energy (k) constant was in Anantnag soil. The Langmuir isotherm best explains the adsorption trend at low adsorbent concentrations. A significant correlation among b1, clay, and cation exchange capacity was observed. Linear affiliation was observed in all the soils at all concentration, indicating that B adsorption data conform to the Freundlich equation. Soils with greater affinity for B adsorption, like Sagipora, tended to desorb less B. Boron desorption was positively and significantly correlated with sand content and negatively with clay content and cation exchange capacity. The maximum value of 50.76 mg g^?1 for desorption maxima (Dm) was observed in Sagipora soil, and mobility constant (Kd) was maximum in Khag soil (0.412 ml kg^?1).     

Selenium adsorption in soils as influenced by different anions

Studies on selenium adsorption were conducted on seleniferous and non‐seleniferous soils of north‐west India. Soils were equilibrated with graded levels of Se ranging from 1 to 100 μg ml^—1 tagged with ⁷⁵Se in the presence of sulphate, nitrate and phosphate ions, generally being applied to soils as inorganic fertilizers. The adsorption of Se on different soils, both in the presence and absence of competing anions, increased with increase in the level of Se added. Adsorption of Se conformed to Langmuir equation. In the absence of any competing anions, adsorption maxima of Se for different soils ranged from 270 to 461 μg g^—1. The corresponding values decreased appreciably in the presence of competing anions; per cent decrease ranged from 3 to 21 at 10 μg SO₄‐S ml^—1, from 8 to 40 at 60 μg NO₃‐N ml^—1 and 32 to 56 at 15 μg H₂PO₄‐P ml^—1. The bonding energy of Se in different soils decreased by 33 to 66 per cent in the presence of only phosphate ions. The changes in bonding energy were inconsistent in the case of nitrate and sulphate ions. At equal concentration of added P and Se, the amount of P adsorbed was 2 to 3 times the amount of Se adsorbed. With increasing concentration of Se, greater amounts of S were released in the equilibrium solution. The distribution coefficients (K_d) decreased significantly in the presence of different anions; the effect was conspicuous in the case of phosphate ions.     

Effect of Soil Properties on Boron Adsorption and Release in Arid and Semi-Arid Benchmark Soils

The adsorption isotherms indicated that the adsorption of boron (B) increased with its increasing concentration in the equilibrium solution. The Langmuir adsorption isotherm was curvilinear and it was significant when the curves were resolved into two linear parts. The maximum value of adsorption maxima (b1) was observed to be 7.968 mg B kg^?1 in Garhi baghi soil and the bonding energy (k) constant was maximum at 0.509 L mg^?1 in Jodhpur ramana soil. The Langmuir isotherm best explains the adsorption phenomenon at low concentrations of the adsorbent, which of course was different for different soils. There was significant correlation between b1 and clay (r = 0.905**), organic matter contents (r = 0.734*), and cation exchange capacity (CEC; r = 0.995**) of soils. A linear relationship was observed in all the soils at all concentration ranges between 0 and 100 mg B L^?1, indicating that boron adsorption data conform to the Freundlich equation. Soils that have a higher affinity for boron adsorption, like Garhi baghi, tended to desorb less amount of boron, that is, 43.54%, whereas Ballowal saunkhari desorbed 48.00%, Jodhpur ramana 48.42%, and Naura soil 58.88% of the adsorbed boron. Boron desorption by these soils is positively and significantly correlated with the sand content (r = 0.714**) and negatively with clay content (r = ?0.502*) and CEC (r = ?0.623**). The maximum value of 37.59 mg kg^?1 for desorption maxima (Dm) was observed in Garhi baghi soil and also a constant related to B mobility (Kd) was found to be maximum in Garhi baghi (0.222 L kg^?1) soil Note: *P<0.05; ^**P<0.01.     

STUDIES ON SOIL COPPER

Adsorption isotherms were determined for the specific adsorption of copper by soils and soil constituents. Adsorption was found to conform to the Langmuir equation. The Langmuir constants, a (adsorption maximum) and b (bonding term), were calculated. Soils were found to have specific adsorption maxima at pH 5.5 of between 340 and 5780 μg g^?1, and a multiple regression analysis revealed that organic matter and free manganese oxides were the dominant constituents contributing towards specific adsorption. Adsorption maxima for soil constituents followed the order manganese oxides > organic matter > iron oxides > clay minerals, which supported the findings for whole soils. The cation exchange capacities (non-specific adsorption) of the test soils were found to be far greater than the specific adsorption maxima. However, evidence suggests that, for the relatively small amounts of copper normally present in soils, specific adsorption is the more important process in controlling the concentration of copper in the soil solution.     

THE CONTENTS AND SORPTION OF CADMIUM IN SOME AGRICULTURAL SOILS OF ENGLAND AND WALES

Cadmium sorption was measured in 10 agricultural soils with pH ranging from 4.5 to 7.9, and total Cd content from 0.27 to 1.04 μg g^?1 dry soil. With initial Cd concentrations of 0.5 to 100.0 μM, sorption from 0.002 M CaCl₂ was described by the Freundlich adsorption equation but the gradients of the isotherms increased when the initial concentrations were below 0.5 μm. This indicates that there are specific sites of differing sorption energy; differences between soils in the gradients of the isotherms at low initial concentration could largely be accounted for by their contents of ‘free’ Fe₂O₃. When initial concentrations were below 0.5 μm there was a linear relationship between the quantity of Cd sorbed and the final concentration in solution. This relationship held with all soils except that of lowest pH from which there was a net loss of Cd to the solutions. Desorption was measured from three soils with contrasting pH. With the soil of lowest pH, over 80 per cent of sorbed Cd was desorbed to 0.002 m CaCl₂ and up to 30 per cent to 100 or 500 μm solutions of heavy metal chlorides. In contrast, only very small proportions (<1.25 per cent) were desorbed from the other soils with pH 6.7 and 7.8. The results indicate that Cd is strongly sorbed by soils of pH of above 6.0 when added in amounts comparable to additions in sewage sludges or phosphatic fertilizers, and illustrate the importance of liming as a means of reducing the mobility of this metal in soils.     

THE DISTRIBUTION OF LABELLED SUGARS IN SOIL PARTICLE SIZE FRACTIONS AS A MEANS OF DISTINGUISHING PLANT AND MICROBIAL CARBOHYDRATE RESIDUES

Soils of the Countesswells and Insch series incubated with ¹⁴C labelled glucose or plant materials have been separated into clay (< 2 μm), silt, (2–20 μm), fine sand (20–250 μm) and coarse sand (>250μm) fractions and the distribution of individual labelled and unlabelled sugars was determined in each fraction. Both soils contained about 10–15 per cent clay, 18–23 per cent silt and about 60 per cent fine and coarse sand. For all soil samples the concentrations of sugars were usually greatest in the clay, slightly less in the silt, with values in the sand fractions being five or ten times lower, except when fresh plant material was present. In ¹⁴C glucose amended Insch soil, 55 per cent of the radioactivity in sugars (predominantly hexoses) occurred in the clay, 36 per cent in the silt, 3 per cent in the fine sand and 6 per cent in the coarse sand after 28 days incubation. For the Countesswells soil the values were 55, 42, 2 and 1 per cent respectively. In ¹⁴C ryegrass amended soil before incubation. 77 per cent of the radioactivity in sugars (predominantly glucose, arabinose and xylose) was in the coarse sand. After one year's incubation this had fallen to 59 per cent. In soil amended with ¹⁴C cereal rye straw the distribution of radioactivity in sugars after four years incubation was: clay, 21 per cent; silt, 43 per cent; fine sand, 21 per cent; coarse sand, 4 per cent. These distributions were compared with that of the naturally occurring sugars: clay, 31–42 per cent; silt, 40–43 per cent; fine sand, 3–11 per cent; coarse sand, 12–20 per cent.     

Determination of the Residual Metal Binding Characteristics of Soils Polluted by Cd and Pb

Four soils contaminated by Pb-Zn mining, Pb-Zn smelting, sewage sludge application, and clay pigeon shooting, respectively, were evaluated for their ability to attenuate relatively high concentrations of supplied Cd and Pb. The retention characteristics of the polluted soils and ‘background’-unpolluted soils for Cd and Pb, were assessed by batch adsorption experiments and equilibrium dialysis titration of the soil organic component. From the sorption data it was observed that the mining polluted and sewage sludge treated soils showed no significant change in Cd affinity when compared to the unpolluted soils. However, for Pb, the reduction in the slopes in the isotherms of the sludge treated and shot over soils were significant when compared to the background soils – indicating a reduced affinity for Pb. The Cd and Pb complexation capacities of the organic component were reduced in the mining, smelter and shot over soil compared to their respective background soils. However, the complexation capacity for Cd of the sludged soil increased from 1.01 µmol Cd g^-1 of organic matter to 4.38 µmol Cd g^-1 of organic compared to the background soil, but, the stability constant of the organo-metal complex formed was lower (6.05 cf. 6.85).     

STUDIES ON SOIL COPPER

A method based on that used by McAuliffe et al. (1948) for phosphorus was developed for determining isotopically exchangeable copper in soils using the radioisotope ⁶⁴Cu. The authors are confident that, with a few exceptions, isotopic equilibrium in soil/solution systems is attained rapidly enough to overcome possible difficulties resulting from the short half-life of this isotope. For the twenty-four soils examined, amounts of isotopically exchangeable copper were found to be between 0.19 and 12-24 μg g^-I and represented between 2 and 21 per cent of the total soil copper. A correlation test and an experiment involving fractionation of labelled soils both demonstrated that the bulk of the isotopically exchangeable copper was located in the organic-bound fraction. Not all copper specifically adsorbed by organic matter was readily exchangeable with ⁶⁴Cu : for one sample of organic material examined only 20 per cent of the adsorbed copper was isotopically exchangeable after 24 hours equilibration. The corresponding figures for clay materials and oxide material were found to be between 75 and 60 per cent.     

THE REACTION OF FLUORIDE WITH SOILS AND SOIL MINERALS

The reaction of sodium fluoride solution with soils and soil minerals at constant pH has been assessed as a possible single-value characteristic in the classification of soils, particularly those containing significant amounts of poorly ordered inorganic material. A suitable method involves reaction of the soil or clay at 25°C with 0·85 M sodium fluoride at pH 6·8, the amount of OH^? released after 25 min being taken as the single-value characteristic. There was a statistically significant correlation between the amount of OH^? released and the amount of alumina extracted with cold 5 per cent sodium carbonate solution from both freely drained and poorly drained Scottish soils. The multiple correlation coefficients were improved for freely drained soils by including the dithionite-extracted ferric oxide and the silica soluble in 5 per cent sodium carbonate solution. The procedure is not suitable for surface soils, because of interference by organic matter, or for carbonate-containing soils unless carbonate is removed.     

PHOSPHATE ADSORPTION IN ALLOPHANIC SOILS

The kinetics and heats of phosphate adsorption were measured on the <2 μm Na-saturated fractions of three allophanc-rich soils from Japan. Between 50 and 2250 μmol P g^?1 as sodium phosphate were added to the soil fractions at pH 5 and pH 7, and at initial concentrations of 5 and 25 × 10^?4m to avoid aluminium phosphate precipitation. An initial ‘instantaneous’ adsorption associated with exposed sites and, simultaneously, two inverse exponential rates of adsorption on internal and freshly forming external sites were observed. These rates are attributed to changes in the microstructure of allophane and to the desorption of organic matter held on allophanic surfaces. This interpretation is strongly supported by corresponding changes in the heats of adsorption with time. Calorimetry clearly indicates that when very large amounts of phosphate are added, new and very reactive surfaces are progressively exposed. More phosphate was adsorbed when the soil was acid and when the soil contained less organic matter.     

Effects of acetylene on nitrification and denitrification in two soils during incubation with ammonium nitrate

A loam from the Frilsham and one from the Wickham Series were incubated at 50 and 90 per cent of their water contents at saturation with 100 μg NH₄NO₃-N_g^?1 soil in the presence and absence of C₂H₂ (0.5 per cent, v/v). Acetylene inhibited nitrification in both soils, but had no effect on mineralization of N. No denitrification (measured as the production of N₂O in the presence of C₂H₂) occurred during incubation at 50 per cent saturation. At 90 per cent saturation, denitrification resulted in a loss of 28.4 and 36.7 μg N_g^?1 after 48 h from the Frilsham and Wickham soils, respectively. The concurrent inhibition of nitrification had no effect on the extent of denitrification at this time. In the Wickham soil, NO₃^? was exhausted after 168 h incubation in the presence of C₂H₂ and denitrification was underestimated by 13 μg N_g^?. The data suggested that concurrent inhibition of nitrification during measurement of denitrification using the C₂H₂ inhibition technique is most likely to affect the estimate of denitrification loss when NO₃^?supply is limited by the inhibition of nitrification.     

Survival of Pseudomonas solanacearum biovars 2 and 3 in soil: Effect of moisture and soil type

The survival of Pseudomonas solanacearum biovars 2 and 3 in three soils, a Nambour clay loam, a Beerwah sandy loam and a Redland Bay clay, was compared at pressure potentials of ?0.003, ?0.05 and ?0.15 kPa. The soils were inoculated with mutants of P. solanacearum biovars 2 and 3, resistant to 2000 μg streptomycin sulphate ml^?1 and their survival measured every 6 weeks for 86 weeks in the clay loam and clay and for 52 weeks in the sandy loam. Soil populations declined with the initial drying necessary to bring the soil moisture to the specific pressure potentials; the initial counts for biovar 2 varied between 0.20 and 2.00 × 10⁹ cfu g^?1 soil and for biovar 3 between 0.17 and 1.29 × 10⁹ cfu g^?1 soil.The population decline in soil maintained at a constant pressure potential was expressed as the rate of population decline. Biovar 2 declined more rapidly than biovar 3. The rate of population decline of each biovar at ?0.003 and ?0.05 kPa was greater in clay loam than in sandy loam and at all pressure potentials it was greater in clay loam and sandy loam than in clay. There was also a tendency for the rate of population decline of both biovars to decrease in the drier soil treatments.     

THE HIGH- AND LOW-ENERGY PHOSPHATE ADSORBING SURFACES IN CALCAREOUS SOILS

The two-surface Langmuir equation was used to study P adsorption by 24 calcareous soils (pH 7.2-7.6; 0.8-24.2 per cent CaCO₃) from the Sherborne soil series, which are derived from Jurassic limestone. High-energy P adsorption capacities (x″_m) ranged from 140–345 μg P/g and were most closely correlated with dithionite-soluble Fe. Hydrous oxides therefore appear to provide the principal sites, even in calcareous soils, on which P is strongly adsorbed (x″_m 6–51 ml/μg P). The low-energy adsorption capacities (x″_m) ranged from 400–663 μg P/g and were correlated with organic matter contents and the total surface areas of CaCO₃ but not with per cent CaCO₃, pH, or dithionite-soluble Fe. Total surface areas of CaCO₃ in the soils ranged from 4.0 to 8.5 m²/g soil. Low-energy P adsorption capacities agree reasonably with values (100 pg P/m²) for the sorption of phosphate on Jurassic limestones but phosphate was bonded much less strongly by soil carbonates (k″= 0.08–0.45 ml/μg P) than by limestones (k～10.0 ml/μg P). Low-energy P adsorption in these soils is tentatively ascribed to adsorption on sites already occupied by organic anions (and probably also by bicarbonate and silicate ions) which lessen the bonding energy of co-adsorbed P.     

Zinc Diffusion and Self-Diffusion Coefficient in Alkaline Soils as Affected by Soil Properties and Zinc Carrier

The apparent diffusion coefficients, D_p/b+ø, of Zn and ZnEDTA were linear functions of added Zn, and were related to the adsorption and fixation capacities of soils rather than their pH. Lower apparent diffusion coefficient values were found in an Haplustoll soil that had higher clay and humus contents inspite of its lower pH. At comparable rates of added Zn, the apparent diffusion of ZnEDTA was 930–1010 (Bakyria), 700–1330 (Dirab), and 730–1880 (Baha) times that of Zn in the soils. The adsorbed Zn per cm³ of soil/Zn per cm³ of the equilibrium solution at the water content existing in the diffusion experiment approximated the capacity factor and was determined by extrapolation. The self-diffusion coefficient of Zn in Baha soil (5 × 10^?7 cm²sec^?1) of higher clay and water content was higher than in Bakyria or Dirab soil (2 × 10^?7 cm²sec^?1). These values were similar to the self-diffusion coefficient of P in soils of similar texture at similar water content.     

A LANGMUIR TWO-SURFACE EQUATION AS A MODEL FOR PHOSPHATE ADSORPTION BY SOILS

For forty-one soils (pH > 5.0) from southern England and eastern Australia, the Langmuir equation was an excellent model for describing P adsorption from solutions < 10^-3M P, if it was assumed that adsorption occurs on two types of surface of contrasting bonding energies. For most of these soils, which were relatively undersaturated with P, this equation may be written as: where x = adsorption, k = adsorption/desorption equilibrium constant, x_m= monolayer adsorption capacity, and c = equilibrium solution concentration. The relative magnitude of the parameters for each surface were approximately: x_m= 0.3 x^″_m=0.3 and k′= 100 k. More than 90 per cent of the native adsorbed P occurs on the high-energy surface in most soils.     

Influence of methanol and hexane on soil adsorption of atrazine

The increasing frequency of chemically contaminated groundwater, occurring as a result of improperly managed waste disposal or accidental spills, presents a need for research on the fate of chemical mixtures in the soil. The batch equilibration technique was used to measure adsorption of ¹⁴C ring-labeled atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine) for a Palouse silt loam (Pachic Ultic Haploxeroll) and a Pembroke silty clay loam (Typic Paleudalf). The solution phase consisted of mixtures of methanol-water and hexane-water containing up to 33.3 % organic solvent by volume. Aqueous solubility limited atrazine concentrations to 100 μmol L^?1 except for an additional isotherm determined in 33.3 methanol-water at up to 1542 μmol L^?1 The Freundlich adsorption coefficient indicated that the Palouse adsorbed more atrazine than the Pembroke with K values of 4.95 and 0.54, respectively. Both soils showed a significant decrease in K as the percentage methanol increased. Adsorption isotherms from a 33. 3 methanol-water system were of the Freundlich type for atrazine concentrations of 0.25 to 1542 μmol L^?1. In the hexane-water systems, K decreased as the fraction of hexane increased and the Pembroke soil adsorbed less atrazine than the Palouse soil. These results suggest that the introduction of nonaqueous solvents such as methanol and hexane decreased adsorption and increased the potential for atrazine mobility.     

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     

ADSORPTION OF HERBICIDE-DERIVED p-CHLOROANILINE RESIDUES IN SOILS: A PREDICTIVE EQUATION

Relationships between the adsorption of p-chloroaniline and the original adsorbate concentration were investigated for five soils ranging in organic matter content from 1.7 to 8.1 per cent and in clay content from 0.5 to 21 per cent. Adsorption data were analyzed applying the linear form of the Freundlich equation. To evaluate the general relationship between adsorption of p-chloroaniline by soils and the solution concentration (C₀), values of partition coefficient (Kp), reflecting the magnitude of distribution of chemical at equilibrium between soil colloids and solution were calculated. The experiments showed that the regression parameters were significantly correlated with the soil organic matter content. A comparison of the experimental results obtained with other soils and the calculated values gave satisfactory agreement.     

ABSTRACT of the Articles Printed in Journal of the Science of Soil and Manure,Japan

A contrasting occurrence of clay minerals was found within a soil profile which was derived from volcanic materials in the suburbs of Fukuoka-city, Northern Kyushu. The soil profile is located on an isolated terrace, and the morphological characteristics of the soil correspond exactly to Andosols, so-called Kuroboku soils or Humic Allophane soils.

The clay fraction of upper horizons of the soil consists largely of alumina-rich gel-like materials, gibbsite, and layer silicates such as chlorite and chloritevermiculite intergrades, while that of lower horizons is composed of allophane and gibbsite or halloysite. There was no positive indication of allophane in the upper horizons. Corresponding with the clay mineralogical composition, quartz is abundant in the fine sand fraction of the upper horizons, while the mineral is very scarce or none in the lower horizons, suggesting a close relation between the petrological nature of parent volcanic materials and the mineralogical composition of weathering products. The dominant clay mineral in the volcanic 1.10il might be dependent on the petrological nature of parent materials, and allophane is mostly formed from andesitic materials, and alumina-rich gel-like materials and layer silicates have come from quartz andesitic materials. Allophane would transform to gibbsite or halloysite according to weathering conditions, and aluminarich gel-like materials change to gibbsite under a well-drained condition.

The soil materials have been so greatly weathered that some horizons contain gibbsite of even more than 40 per cent or halloysite over 70 per cent. The morphology and mineralogy are quite similar to so-cailed “non-volcanic Kuroboku soils.”     

Phosphorus Management of Lucerne Grown on Calcareous Soil in Turkey

ABSTRACT

Lucerne or alfalfa (Medicago sativa L.) is grown as a forage crop on many livestock farms. In calcareous soils in eastern Turkey, lucerne production requires phosphorus (P) additions as the soils are naturally P deficient. Phosphorus sorption isotherms were used to estimate P fertilizer needs for lucerne grown for two years in a 3-cut system on a calcareous P deficient Aridisol in eastern Anatolia, Erzurum province, Turkey. Annual P applications ranged from 0–1200 kg P ha^?1. The Langmuir two-surface adsorption equation was used to derive the maximum P sorption capacity of unamended soil and to determine soil solution P, maximum buffer capacity (MBC), equilibrium buffer capacity (EBC), and P saturation at the optimum economic P rate (OEPR) for dry matter (DM) production. Soils were tested for Olson P at the onset of the study and after two years of P applications. In both years, tissue was analyzed for P content at flowering prior to first cutting. The OEPR (2-year average) was 754 kg P ha^?1 yr^?1 corresponding with a soil solution P concentration of 0.30 mg L^?1, a DM yield of 8725 kg DM ha^?1, and $528 ha^?1 annual profit. The P content of leaves at flowering increased linearly with P application beyond 100 kg P ha^?1 and was 3.2 g kg^?1 P at the OEPR. The unfertilized soil had an EBC, MBC, P saturation, and X_max of 3304 mL g^?1, 3401 mL g^?1, 6%, and 1086 mL g^?1, respectively, whereas two years of fertilization to the OEPR decreased EBC and MBC to 358 mL g^?1 and 540 mL g^?1, and increased P saturation and Olsen P to 56% and 32 mg kg^?1, respectively. These results suggest a P saturation >50% or Olsen P >30 mg kg^?1 are needed to maintain an optimum soil solution concentration of 0.30 mg L^?1 in this calcareous Aridisol. Similar studies with different soils and initial soil test P levels are needed to conclude if these critical soil test values can be applied across the region.