Effects of cations and anions on iron and manganese sorption and desorption capacity in calcareous soils from Iran

This study investigated the effect of cations and anions on the sorption and desorption of iron (Fe) and manganese (Mn) in six surface calcareous soil samples from Western Iran. Six 10 mM electrolyte background solutions were used in the study, i.e., KCl, KNO₃, KH₂PO₄, Ca(NO₃)₂, NaNO₃, and NH₄NO₃. NH₄NO₃ and NaNO₃ increased the soil retention of Fe and Mn, whereas Ca(NO₃)₂ decreased the soil retention of Fe and Mn. Iron and Mn sorption was decreased by NO₃ ^? compared with H₂PO₄ ^? or Cl^?. The Freundlich equation adequately described Fe and Mn adsorption, with all background electrolytes. The Freundlich distribution coefficient (K _F) decreased in the order H₂PO₄ ^? > Cl^? > NO₃ ^? for Mn and H₂PO₄ ^? > NO₃ ^? > Cl^? for Fe. The highest sorption reversibility was for Fe and Mn in competition with a Ca²⁺ background, indicating the high mobility of these two cations. A MINTEQ speciation solubility model showed that Fe and Mn speciation was considerably affected by the electrolyte background used. Saturation indices indicated that all ion background solutions were saturated with respect to siderite and vivianite at low and high Fe concentrations. All ion background solutions were saturated with respect to MnCO_3(am), MnHPO₄, and rhodochrosite at low and high Mn concentrations. The hysteresis indices (HI) obtained for the different ion backgrounds were regressed on soil properties indicating that silt, clay, sand, and electrical conductivity (EC) were the most important soil properties influencing Fe adsorption, while cation exchange capacity (CEC), organic matter (OM), and Mn-DTPA affected Mn adsorption in these soils.     

Distribution of nitrogen forms in surface sediments of lakes from different regions,China

The characteristics of nitrogen fractions in the surface sediments of lakes from Eastern Plain Region, Yunnan-Guizhou Plateau Region, Northeast China Region, Qinghai-Tibet Plateau Region and Mongolia-Xinjiang Plateau Region were investigated and the differences of five lake regions on nitrogen fractionation were discussed. The results indicated that organic nitrogen (N_org) was the major nitrogen fraction accounting for 76.38–92.02 % of N_tot in sediments. The rank order of average N_org and N_tot of sediments in five lake regions was: Yunnan-Guizhou Plateau Region > Northeast China Region > Mongolia-Xinjiang Plateau Region > Qinghai-Tibet Plateau Region > Eastern Plain Region. The exchangeable nitrogen had a similar distribution as organic nitrogen in the studied sediments. NH₄ ⁺–N is the main exchangeable nitrogen of sediments in the studied lakes except in Lake Qinghai and Lake Yamdrok which contained higher nitrate concentrations than ammonium. Fixed ammonium (N_fix) in the sediments of studied lakes was irregularly distributed with the values ranging from 99.45 to 329.02 mg/kg. TOC was significantly and positively correlated with ammonium, nitrate, N_org and N_tot, while N_fix was negatively correlated with nitrate probably due to electrostatic attraction between N_fix and nitrate in layers of sediments.     

Mercury concentration in some calcareous soils of western Iran with a focus on pedological evolution and weathering process

The aim of this study was to evaluate total mercury concentration and its lithogenic and exogenic fractions in some calcareous soils of western Iran, where water contamination and bioaccumulation of mercury have been reported in the bottomland’s reservoir. In particular, we investigated soil physico-chemical properties and weathering conditions related to lithogenic and exogenic fractions of mercury for two groups of calcareous soils with a known comparative pedological evolution and weathering condition that was evident in the presence or absence of underlying layers of accumulated clay. Our results showed that the total mercury content of the studied soils ranged from 45.40 to 830.36 with a mean of 486.81 μg kg^?1. Furthermore, calculation of mercury fractions revealed that lithogenic and exogenic fractions vary slightly according to the three reference elements (Fe, U and Nb) used in the calculations for the two groups of studied soils. The results also illustrated that most of the mercury content is of exogenic origin; therefore, total mercury variations are closely related to the content of exogenic mercury, while the lithogenic fraction exhibited no relationship with total mercury concentration. Moreover, application of the weathering indexes of Parker and the CaO/ZrO₂ molar ratio supported the dependence of lithogenic mercury accumulation on weathering intensity in the studied calcareous soils. However, the significance of this relationship is stronger for more weathered calcareous soils; in such cases, fine-particle fractions are more developed, which encourages carrier phases such as organic materials and iron oxyhydroxides to become involved in more efficient fixation of mercury. Nevertheless, the formation of underlying layers of accumulated clay, i.e. argillic horizons, may restrain fixation of exogenic mercury by limiting its atmospheric input.     

Effect of addition of organic residues on phosphorus release kinetics in some calcareous soils of western Iran

We investigated the effects on phosphorus (P) release of the addition of potato, wheat, and sunflower residues and fruit compost to five calcareous soils. Residue was added at the rate of 20 g kg⁻¹. After 2 months of incubation, P values in control and amended soils were used for kinetic studies and fractionated by a sequential extraction procedure. The relative contribution of available P fraction (KCl-P) increased from 1.4% in control soils to 1.8%, 1.9%, 2.2%, and 2.3% in soils amended by fruit, wheat, potato, and sunflower residue addition, respectively, indicating that organic residues increased P in this fraction. In soils amended with different residues, the percentage of Olsen-P released over 86-h successive extractions with 0.01 M CaCl₂ ranged from 57.6% for fruit residue addition (average of five soils) to 60.5% for potato residue addition. The ability of residues to release P depended on the soil properties, with 21.9 mg kg⁻¹ (average of all residues) released to soil 2 and 77.4 mg kg⁻¹ released to soil 4. Also residues behaved differently, with 31.5 mg kg⁻¹ (average of five soils) released by fruit residues and 40.0 mg kg⁻¹ released by sunflower residues. Release of P was best described by a parabolic diffusion model. The corresponding rate constant (mg kg⁻¹ h^−1/2) for P release for amended soils, defined as the release rate averaged for five soils, was found to decrease in the order: potato (2.73) > sunflower (2.61) > wheat (2.56) > fruit (2.50). The present study demonstrates that addition of residues improves P availability of these calcareous soils by increasing extractable P and the release rate and could be an alternative, indigenous source of P. However, the increase in P availability and the release rate following organic residue application suggests high potential mobility to water sources.     

Experimental investigation on aluminum release from haplic acrisols in southeastern China

A sequential dissolution technique and a prolonged extraction method were used to investigate aluminium (Al) release from 4 Haplic Acrisols in southeastern China. The results show that the order of acidification of the 4 soils is: Tunxi soil>Yongchun soil>Shengxian soil>Ninghai soil. The amount of exchangeable Al is directly proportional to the extent of soil acidification. Al was released from both organically bound and inorganic Al pools after acid input. During several initial cycles of extraction the release of Al was mainly from the weakly organically bound Al pool. After prolonged extraction, Al release from the inorganic Al pool became more important to the total dissolved Al due to a rapid depletion of the weakly organically bound Al pool. The sizes of readily reactive Al pools in the Ninghai soil and Shengxian soil are larger than in the Yongchun soil and Tunxi soil. Al released from the inorganic Al pool in the Ninghai soil, Shengxian soil and Yongchun soil after 20 cycles of extraction was higher than from the organically bound Al pool, whereas the opposite was the case for the Tunxi soil. A low saturation of Al binding on soil organic matter (SOM) does not necessarily lead to a low Al release as in the case of the Shengxian soil. Also a relatively high saturation does not necessarily ensure a large Al release from the Al pool as in the case of the Tunxi soil and Yongchun soil. Once both organically bound and inorganic Al pools are depleted of readily reactive Al phases due to high soil acidification, Al dissolution would be small even under strong acid input. The high concentration of aqueous Al after rapid Al release from the weakly organically bound Al pool and subsequent depletion of the pool may have significant ecological and environmental effects.     

Transformation of metal speciation in purple soil as affected by waterlogging

This study was conducted to investigate the effect of waterlogging on copper, lead and cadmium fractionation in Chinese purple soil. Heavy metals were added to purple soil at 80 % field capacity and waterlogging regimes as nitrate salts of 500 mg kg^?1 of copper and lead, and 5 mg kg^?1 of cadmium. Metals in the incubated soil samples were fractionated termly from 1 to 35 days by the sequential extraction procedure. Under both treatments, the heavy metals spiked in the soil were transformed slowly from the exchangeable fractions into more stable fractions, whereas their residual fractions barely changed. The transformation process of exchangeable fraction in soil was estimated by Elovich kinetic equation for the above incubation periods, and the constant B in Elovich equation was applied to reflect the transformation rates of metal speciation. It was found that waterlogging incubation could immobilize heavy metals, resulting in decreased lability and availability of the metals in purple soil. The effect of waterlogging on the redistribution of heavy metals in purple soil might be mainly related to the changes of pH, potential redox and hydrous oxides in varying soil-water systems.     

Comparison of extractability of Cd, Cu, Pb and Zn with sequential extraction in contaminated and non-contaminated soils

Various extraction procedures were employed for measuring extractable concentrations of potential toxic elements in soil. The extractability of Cd, Cu, Pb and Zn in four contaminated and four non-contaminated soils of Japan, was compared by single extraction (CaCl₂, DTPA, NH₄Cl, 0.1 M HCl and 1 M HCl ) and sequential extraction procedures [(six operationally defined chemical phases, viz. water soluble (Fl), exchangeable (F2), carbonate (F3), oxide (F4), organic (F5) and residual (F6) fractions)]. Extractability of metals from soils samples varied depending on metals and/or extradants used. Among the extradants, 1 M HCl extracted the largest proportion of Cd (79 to 96% of total), Cu (61 to 83%), Pb (51 to 99%) and Zn (23 to 52%) from soils followed by 0.1 M HCl, NH₄Cl, DTPA and CaCl₂. In all the extradants, the proportion of extractability of metals was higher in the contaminated soils than the non-contaminated soils. Regardless of soils and extradants, relative extractability was higher for Cd as compared to other three metals. The use of 1 M HCl may be recommended for first-level screening of soil contamination with heavy metals. The other four weak extradants are believed to provide a better assessment of bioavailable/mobile metals content in soils than 1 M HCl extradant. However, 0.1 M HCl mobilized all four metals irrespective of soil types, therefore, might be the best choice if only one extradant is to be used. The sequential extraction procedures showed 22 to 64% of total Cd was in the mobile fraction (sum of Fl to F3), while the corresponding values for Cu, Pb and Zn in this fractions were 2 to 23% suggesting higher mobility of Cd than other three metals. The single extraction procedures are simple and easy to perform and obtained results are comparable with sequential extraction procedure.     

Using soil survey data for series-level environmental phosphorus risk assessment

Choosing soil series scale for assessing phosphorus (P) retention and release characteristics may help relate routinely collected series-specific soil survey data with P retention and aid in designing series-specific P management strategies. Phosphorus retention and release characteristics of pedons collected from two benchmark upland soil series (Berks and Monongahela) and two floodplain (Huntington and Lindside) soil series of West Virginia (USA) were assessed by evaluating P sorption capacity (PSC, Langmuir method) and its major determinants, and effect of different levels of degree of P saturation (DPS) and soil test P (STP, Mehlich-1 P) on the desorbable P (0.01 M CaCl₂-extractable) concentrations. The PSC of the two floodplain soils, Huntington and Lindside, was similar but lower than PSC of upland Berks and Monongahela soils. However, thicker A horizons of Huntington and Lindside soils may compensate for their lower PSC. The B horizons exhibited higher PSC than A horizons. However, slow permeability and thinness of such horizons may discount the higher PSC effect. Relationship of PSC with ammonium oxalate extractable Al (AOX-Al) and Fe (AOX-Fe), dithionite–citrate–bicarbonate extractable Al (DCB-Al) and Fe (DCB-Fe), total C, clay content, and pH [soil:water ratio 1:1 (pH-water) and soil:0.01 M CaCl₂ solution ratio 1:2 (pH-CaCl₂)] showed that in general all except Fe and total C influenced PSC significantly. Aluminum associated with crystalline clay minerals particularly affected PSC, especially of upland soils. Most of the soils did not release considerable P even beyond the conventional critical limit of 25 % DPS for well-drained soils. DPS-desorbable P relationships, though, reflected poor reliability of DPS as an environmental index. At a given DPS and STP, surface horizons released more P than their subsurface counterparts and thus reflected the net sink character of subsurface horizons. Most of the soils did not show considerable release of P even beyond agronomically high STP levels (>23 mg kg^?1). The study provides an economical alternative to time and money-intensive lysimetric studies for assessing subsurface P loss. It reveals the workability of integrating environmental P studies with soil survey data and superiority of integrated assessment of environmental indices of P over the use of any single index.     

Desorption of tetracycline from montmorillonite by aluminum,calcium, and sodium: an indication of intercalation stability

As the uptake of cationic drugs, such as tetracycline (TC), was attributed to cation exchange, the stability of adsorbed TC on a Ca-montmorillonite SAz-2 was studied using cationic solutions of different valence charges under different pH conditions. At the initial loading of 356 mg g^?1, the amounts of TC desorbed by 0.05 M AlCl₃, CaCl₂, and NaCl were 133 ± 4, 83 ± 6, and 50 ± 4 mg g^?1, respectively, or 37, 23, and 14 %. However, when the amount or percentage of TC desorbed was normalized to the equivalence of each cation, the values were in the range of 44–50 mg g^?1 or 11–14 % per 10 mmol of charge. The kinetics of TC desorption were moderately fast and almost reached equilibrium in 6 h. The results followed the pseudo-second-order kinetic model with reaction rate in the order of AlCl₃ > CaCl₂ > NaCl at a higher initial TC loading level. The total amount of TC desorbed after five desorption cycles followed the order of AlCl₃ > CaCl₂ > NaCl, too, suggesting that cations with higher positive charges, thus, less hydrated, are preferred to remove adsorbed cationic drugs. The FTIR analyses showed larger band shift when Al³⁺ was used as the desorbing reagent. The XRD patterns before and after TC desorption revealed no changes in basal spacing, even after five desorption cycles, suggesting that the removal of TC from SAz-2 was largely from the external surfaces.     

Sorption and distribution of adsorbed metals in three soils of India

The mobility and bioavailability of heavy metals depends on the metal retention capacity of soil and also on the geochemical phases with which metals are associated. Laboratory batch experiments were carried out to study the sorption and distribution of Cd, Ni and Pb in 3 soils differing in their physicochemical properties from India: Oxyaquic Haplustalf (SL1), Typic Haplustalf (SL2) and Typic Haplustert (SL3). The heavy metal adsorption was studied by isotherms and the distribution coefficient (K_D) for each metal was obtained from the linear regressions of the concentration of metal remaining in equilibrium solution and the amount adsorbed. In general, the sorption capacity for all the metals decreased in the order: SL3>SL2>SL1. Among metals, the sorption capacity in all the soils decreased in the order: Pb>>Ni>Cd. Distribution of sorbed metals at various equilibrating concentrations was studied by sequential extraction. Results showed significant differences in the distribution of metals in these soils. At higher additions (such as 200 μM l⁻¹) most of the metals were extracted in their more mobile fractions, exchangeable and/or inorganic in contrast to their original partitioning in soils, where they were preferentially associated with the less mobile residual fraction. Largest percentages of metals extracted in the exchangeable fraction corresponded to those soil–metal systems with smaller K_D values, e.g. Cd, Ni and Pb in SL1 and Cd and Ni in SL2. In neutral and alkaline soils (SL2, pH=7.1, and SL3, pH=8.6) Pb was predominantly extracted from the inorganic fractions and this corresponded to higher K_D values for Pb in these soils. The predominance of metals associated with the exchangeable fraction together with low K_D values indicates higher mobility of metals retained in the acidic soil (SL1, pH=5.2) compared with the others.     

Impact of municipal compost on soil phosphorus availability and mineral phosphorus fractions in some calcareous soils

The phosphorus (P) resources worldwide are limited, and the prices of commercial P fertilizer continue to increase. Therefore, the use of P containing wastes is important for P recycling in agriculture. The P fractionation methods have been widely applied to characterize the effect of land use practice on soil P dynamics. Information about effect of organic manures on available P and inorganic P (P_i) fractions in calcareous soils of Chaharmahal va Bakhtiari province is limited. The objectives of this research were to study the effect of municipal compost (MC) on available P and P_i forms in five calcareous soils. Municipal compost was applied at the rates of 0, 0.5, 1.0, 1.5 and 2.0% (w/w). Samples were incubated at 25?±?1°C and 20% moisture content for 150?days. At the end of incubation, available P in MC-treated soils was extracted by Olsen, AB-DTPA and 0.01?M CaCl₂ methods. Also, phosphorus was fractionated chemically into labile P (LP), non-occluded P(NP), re-adsorbed P (RP), occluded P (OP), calcium phosphates (CaP) and residual P. The results showed that there was a linear increase in soil available P with MC application. There was a significant positive relationship between Olsen-P, AB-DTPA-P and 0.01?M CaCl₂-P, and MC additions with slopes ranged from 0.471 to 0.583, 0.032 to 0.106, and 0.033 to 0.081, respectively. The increase in soil test P (STP) from MC additions was not related to the initial STP of the soils. A sharp increase in LP, NP and CaP and decrease in residual P concentration occurred in all soils with MC application. It can be concluded that MC applied to calcareous soils may enhance P nutrition of plants. Furthermore, applied P partitioning into the relatively available forms means the potential erosion losses of P to streams and other bodies of water.     

Amendments affect lead mobility and modulated chemo-speciation under different moisture regimes in normal and salt-affected lead-contaminated soils

The total lead content in the soil itself is insufficient as a measure to indicate the actual environmental risks related to the presence of lead in the soil. Understanding the mobility of lead and its chemical speciation in soil solution is of great importance for accurately assessing environmental risks posed by lead. Therefore, a laboratory study was carried out to evaluate the effect of inorganic amendments (gypsum, rock phosphate and di-ammonium phosphate) on lead mobility and chemical speciation under different moisture regimes (flooding regime and 75 % field capacity) in normal and salt-affected lead-contaminated soils. After 2, 7, 15, 30, 100 and 110 days of incubation, pore water samples were collected by using Rhizon soil moisture samplers. In order to estimate the chemical speciation of lead in pore water, Visual MINTEQ 3.0 modeling approach was used. The results showed that presence of free Pb²⁺, PbCl⁺, Pb(SO₄) ₂ ^2? , and PbH₂PO₄ ⁺ was significantly (P ≤ 0.05) affected by the soil moisture regime, incubation time and applied amendments in lead-contaminated soils. The Visual MINTEQ 3.0 predicted free Pb²⁺ species concentration was found higher in lead-contaminated soils, while PbCl⁺ was more pronounced in salt-affected soils. Gypsum increased the occurrence of Pb(SO₄) ₂ ^2? , while di-ammonium phosphate and rock phosphate enhanced the PbH₂PO₄ ⁺ species formation and decreased free Pb²⁺ species in pore water. Thus, gypsum is the most effective in reducing lead and free Pb²⁺ species concentrations in the pore water under different soil moisture regimes and incubation times in normal and salt-affected lead-contaminated soils.     

Using chemical analysis and modeling to enhance the understanding of soil solution of some calcareous soils

The chemistry of soil solutions can be altered by human activities, due to the intense agricultural and husbandry, leading to leaching of nutrients and subsequently elevating ground water levels. Multivariate statistical and inverse geochemical modeling techniques were used to determine the main factors controlling soil solution chemistry of calcareous soils. In this research, a total of 21 calcareous soils was characterized and assessed for soil solution using soil column. The major cations in the studied soil solutions were in the decreasing order as Ca²⁺ > Mg²⁺ > Na⁺ > K⁺. The anions were also arranged in decreasing order as HCO $ _{3}^{ - } $  > Cl $ ^{ - } $  > SO $ _{4}^{2 - } $  > NO $ _{3}^{ - } $ . Concentrations of NO $ _{3}^{ - } $ , P, and K⁺ in soil solutions were in the range of 6.8–307.5 mg l^?1 (mean 63.2 mg l^?1), 5.0–10.4 mg l^?1 (mean 5.9 mg l^?1), and 2.8–54.6 mg l^?1 (mean 11.3 mg l^?1), respectively. Results suggest that the concentration of P in the soil solutions could be primarily controlled by the solubility of dicalcium phosphate dihydrate and dicalcium phosphate. Interactions between soil properties and observed solubility of nutrients were described, and put into empirical multivariate formulations. Obtained equations contained electrical conductivity (EC) as a key factor in determining nutrients solubility. Inverse geochemical modeling of soil solution using PHREEQC indicates the dissolution of calcite, anhydrite, halite, CO₂ (g), N₂ (g), and hydroxyapatite, and precipitation of sulfur. Cation exchange between Ca²⁺, Mg²⁺, K⁺ and Na⁺ occurred with Mg²⁺ and K⁺ into the solution, and Ca²⁺ and Na⁺ out of the solution. Determination of soil solution will improve soil management in the area, and preventing groundwater deterioration.     

Reclamation of calcareous saline–sodic soil using different amendments: Time changes of soluble cations in leachate

Soil salinity and sodicity are escalating problems worldwide, especially in arid and semiarid regions. A laboratory experiment was conducted using soil column to investigate leaching of soluble cations during reclamation process of a calcareous saline–sodic soil (CaCO₃?=?20.7%, electrical conductivity (EC)?=?19.8 dS m^?1, sodium absorption ratio (SAR)?=?32.2[meq L^?1]^0.5). The amendments consisted of control, cattle manure (50 g kg^?1), pistachio residue (50 g kg^?1), gypsum (5.2 g kg^?1; equivalent of gypsum requirement), manure + gypsum and pistachio residue + gypsum, in three replicates which were mixed thoroughly with the soil, while sulfuric acid as an amendment was added to irrigation water. To reflect natural conditions, after incubation period, an intermittent irrigation method was employed every 30 days. The results showed that EC, SAR, and soluble cations of leachate for the first irrigation step were significantly higher than those of the subsequent leaching runs. Moreover, the concentration of removed soluble cations was lower for the control and gypsum-treated soils. It was found that among applied amendments, treatments containing cattle manure showed higher concentrations of sodium, calcium, and magnesium in the leachate, while due to pistachio residue application, further amount of potassium was removed out of soil column. The addition of pistachio residue resulted in the highest reduction in soil salinity and sodicity since the final EC and exchangeable sodium percentage dropped to 18.0% and 11.6% of their respective initial values, respectively. In the calcareous soil, solubility of gypsum found to be limited, in contrast, when it was added in conjunction with organic amendments, greater amounts of sodium were leached.     

Effect of sheep manure and EDTA on the leaching of potassium from heavy metals contaminated calcareous soils

In this study, we examined the movement of potassium (K) in columns of contaminated calcareous soils by sheep manure and ethylene diamine tetraacetic acid (EDTA). Glass tubes, 4.9 cm in diameter and 40 cm in length, were packed with contaminated soils. The resulting 20-cm long column of soil had a bulk density of 1.3–1.4 g cm⁻³. Columns were leached with distilled water, 0.01 M EDTA, 0.01 M CaCl₂, and sheep manure extract solutions. The amounts of K leached varied considerably between different soils (sandy loam and loamy sand) and leaching solutions. The amount leached with EDTA solution, varied from 7.2 to 66.7% of the extractable K when 20 pore volumes had passed through the column. The breakthrough curves of K in the EDTA and CaCl₂ were approximately similar, indicating they have similar ability to displace K from these contaminated calcareous soils. Thus, among leaching solutions application of EDTA and CaCl₂ on contaminated soils might enhance the mobility of K and large amounts of K will be leached.     

Surface complexation model of boron adsorption by calcareous soils

This study aimed to evaluate boron (B) adsorption and the capacity of a surface complexation model for simulating this process in calcareous soils. Ten surface soils were collected from different land use areas in Hamedan, Western Iran, to characterize B sorption by soils. The mean B adsorbed by the sample soils varied from 8.9 to 32.8 %. Two empirical models including linear and Freundlich equations fitted well to the experimental data. The linear distribution (K _d) values varied from 1.32 to 6.86 L kg^?1, while the parameters of Freundlich equation including n and K _Fr ranged from 1.16 to 1.33 and 3.31–16.81, respectively. The comparison of two empirical models indicated that B adsorption followed a nonlinear pattern. The soil organic matter had positive correlations with Freundlich and linear distribution coefficients. However, empirical models were not suitable for explaining the mechanism of B adsorption, so a surface complexation model was used to simulate and predict the B adsorption process. B adsorption modeling was conducted using Visual MINTEQ and PHREEQC, based on the assemblage of major surface components (hydrous ferric oxides, aluminum hydroxides, calcium carbonate, and humic acids). B adsorption was successfully modeled by surface complexation. The significant contribution of organic matter to B complexes was resulted from both experimental data and mechanistic modeling.     

Effect of alkaline solutions on bentonite properties

The influence of alkaline aqueous solutions on the properties of bentonite was investigated to evaluate the performance of bentonitic engineered barriers when contacted with alkaline groundwater. Batch and hydraulic conductivity tests were conducted on Na-bentonite using six different alkaline aqueous solutions. For the batch tests, almost no change in the montmorillonite fraction of the bentonite was observed after reacting with alkaline solutions (pH = 8.4–13.1), regardless of the solution type. On the other hand, aluminosilicate minerals (e.g., albite) were dissolved and secondary minerals (e.g., anorthite) were formed in alkaline NaOH solutions (pH > 13). The cation (Ca or Na) concentration primarily affected the swelling properties of bentonite rather than the pH of the solution, which was comparable to the results of the hydraulic conductivity tests. For the Ca solutions, the hydraulic conductivity of the bentonite specimen to the 0.02 mol/L Ca(OH)₂ solution (6.5 × 10^?9 cm/s) was approximately an order of magnitude lower than that of the bentonite specimen to the 0.02 mol/L Ca(OH)₂ + 1 mol/L CaCl₂ solution (5.0 × 10^?8 cm/s), whereas the hydraulic conductivity to the 0.02 mol/L Ca(OH)₂ + 1 mol/L CaCl₂ solution (pH = 11.3) (5.0 × 10^?8 cm/s) was slightly higher than that to the 1 mol/L CaCl₂ solution (pH_i = 8.4) (4.4 × 10^?8 cm/s). For the NaOH solutions with pH > 13, the hydraulic conductivity of the bentonite specimen decreased with increasing Na concentration, suggesting that the effect of Na concentration was more dominant than that of permeant pH.     

Impact of sewage sludge application on zinc desorption kinetics in some calcareous soils

Sewage sludge usually contains significant amount of Zinc (Zn) and is widely used in agricultural lands. A laboratory experiment was performed to determine Zn desorption characteristics in unamended and amended soils with sewage sludge. Ten calcareous soils were amended with 1 % (w/w) sewage sludge. Amended and unamended soils were incubated at field capacity at 25 ± 1 °C for 1 month. After incubation, the kinetics of Zn desorption in amended and unamended soils were determined by successive extraction with DTPA-TEA (diethylenetriaminepentaacetic acid-triethanolamine) in a period of 1–504 h at 25 ± 1 °C. The results of kinetics study showed that extracted Zn and desorption rate constants in the amended soils were significantly (p < 0.01) higher than in the unamended soils. The results showed that Zn desorption increased from 201 to 343 % in amended soil with respect to unamended soils. The amounts of desorbed Zn in the unamended soils ranged from 3.73 to 8.79 mg kg^?1, while the amounts of desorbed Zn in amended soils ranged from 11.47 to 17.66 mg kg^?1. Desorption kinetics of Zn in two soils conformed fairly well to first-order, parabolic diffusion and power function equations. The results of stepwise regression analysis indicated that calcium carbonate equivalent and clay could be used to estimate Zn desorption characteristics in DTPA-TEA solution in the amended and unamended calcareous soils. It can be concluded that sewage sludge applied to calcareous soils may enhance the source of Zn for the plants.     

Cobalt sorption–desorption behavior of calcareous soils from some Iranian soils

Little research has been done to study the role of soil parameters in cobalt (Co) retention, release and the processes involved in calcareous soils of arid and semi-arid regions. We studied the Co sorption and desorption capacity of various calcareous soils using batch technique. The sorption and desorption behavior of Co varied greatly among the studied soils. The sorbed fraction ranged from 92.3% to 97.2% and from 51.0% to 71.8%, when 5 and 200 mg Co l⁻¹, was added to the soil samples, respectively. Cobalt sorption curves were well fitted with Langmuir, Freundlich, and linear equations. The values of the distribution coefficients obtained from linear equation ranged from 9.5 l kg⁻¹ to 23.4 l kg⁻¹. Desorption experiments resulted in a Co recovery ranged from 3.6% to 11.4%, indicating a low desorption of Co from soils. The results of the geochemical modeling indicated that under low Co addition, the solutions were undersaturated with respect to Co(OH)_2(am), Co(OH)_2(c), Co₃(PO₄)_2(s), CoCl_2(s), CoHPO_4(s), CoCl₂·6H₂O_(s), and CoO_(s), whereas under higher Co addition, the solutions were undersaturated with respect to Co(OH)_2(am), CoCl_2(s), CoCl₂·6H₂O_(s), CoO_(s), CoHPO_4(s), and saturated with respect to Co₃(PO₄)_2(s), and CoCO_3(s). The hysteresis indices indicated that desorption of freshly sorbed Co with 0.01 M CaCl₂ was hysteretic in all soils and low mobility and leaching potential of freshly sorbed Co can be expected from these calcareous soils. Statistical correlations revealed that Co sorption and desorption onto the soils were influenced by the presence of CaCO₃ in soils. These findings suggested that calcareous soils are able to retain strongly Co in which the movement of Co in the soil profile would be negligible. Thus, little risk of groundwater contamination can be expected with Co in these calcareous soils.