Ionic-strength and pH effects on the sorption of cadmium and the surface charge of soils

Two Oxisols (Mena and Malanda), a Xeralf and a Xerert from Australia and an Andept (Patua) and a Fragiaqualf (Tokomaru) from New Zealand were used to examine the effect of pH and ionic strength on the surface charge of soil and sorption of cadmium. Adsorption of Cd was measured using water, 0.01 mol dmp^?3 Ca(NO₃)₂, and various concentrations of NaNO₃ (0.01–1.5 mol dm^?3) as background solutions at a range of pH values (3–8). In all soils, the net surface charge decreased with an increase in pH. The pH at which the net surface charge was zero (point of net zero charge, PZC) differed between the soils. The PZC was higher for soils dominated by variable-charge components (Oxisols and Andept) than soils dominated by permanent charge (Xeralf, Xerert and Fragiaqualf). For all soils, the adsorption of Cd increased with an increase in pH and most of the variation in adsorption with pH was explained by the variation in negative surface charge. The effect of ionic strength on Cd adsorption varied between the soils and with the pH. In Oxisols, which are dominated by variable-charge components, there was a characteristic pH below which increasing ionic strength of NaNO₃ increased Cd adsorption and above which the reverse occurred. In all the soils in the normal pH range (i.e. pH>PZC), the adsorption of Cd always decreased with an increase in ionic strength irrespective of pH. If increasing ionic strength decreases cation adsorption, then the potential in the plane of adsorption is negative. Also, if increasing ionic strength increases adsorption below the PZC, then the potential in the plane of adsorption must be positive. These observations suggest that, depending upon the pH and PZC, Cd is adsorbed when potential in the plane of adsorption is either positive or negative providing evidence for both specific and non-specific adsorption of Cd. Adsorption of Cd was approximately doubled when Na rather than Ca was used as the index cation.     

Effect of soil pH on the sorption capacity of soil organic matter for polycyclic aromatic hydrocarbons in unsaturated soils

Sorption by soil organic matter (SOM) is considered the most important process affecting the bioavailability of hydrophobic organic chemicals (HOCs)in soil.The sorption capacity of SOM for HOCs is affected by many environmental factors.In this study,we investigated the effects of soil pH and water saturation level on HOC sorption capacity of SOM using batch sorption experiments.Values of soil organic carbon-water partition coefficient (K_OC) of six selected polycyclic aromatic hydrocar...     

Influence of electrolyte composition and pH on cadmium sorption by an acid sandy soil

Extraction of soil with CaCl₂, has been recommended as a measure of bioavailability of heavy metals. Interpretation of soil extraction data in terms of plant uptake potential may improve when the chemical behaviour of heavy metals in these extracts is ascertained. The effect of pH, Cd complexation by Cl, and competition between Cd and Ca on Cd sorption was studied at an ionic strength of 0.03 m . Sorption of cadmium was measured in 0.01 m CaCl₂, in 0.01 m Ca(NO₃)₂, in a mixture of 0.02 m NaCl and 0.01 m NaNO₃, and in 0.03 m NaNO₃, at different values of pH ranging from 3.8 to 4.9. Adsorption isotherms were all linear, with a negative intercept on the y-axis. This intercept indicated (linear) desorption of only part of the initial soil Cd content. About 50% of the Cd in solution was complexed in the presence of 0.02 m Cl at ionic strength of 0.03. Due to competition between Cd and Ca, sorption of Cd was reduced by 80% in the Ca-electrolytes as compared with the Na-electrolytes. Sorption was highly sensitive to pH as each 0.5 unit increase in pH resulted in twice as much sorption of Cd. An empirical factor in the sorption equation that accounts for this effect of pH showed a similar response to changes in pH as a mechanistic factor. This mechanistic factor was developed by assuming that Cd and protons sorb onto the same sites and that a two-site Langmuir sorption isotherm for protons was able to describe the titration curve of the soil. This similarity may explain the successful application of the empirical factor in this and previous studies.     

几种有机酸对可变电荷和恒电荷土壤吸附镉的影响

The objectives of this study were to illustrate the reaction processes, to identify and quantify the precipitates formed, and to estimate the porosity losses in order to eliminate drawbacks during remediating monochlorobenzene （MCB） and trichloroethylene （TCE）-contaminated aquifers using the ORC-GAC-Fe^0-CaCO3 system. The system consisted of four columns （112 cm long and 10 cm in diameter） with oxygen-releasing compound （ORC）, granular activated carbon （GAC）, zero-valent iron （Fe^0）, and calcite used sequentially as the reactive media. The concentrations of MCB in the GAC column effluent and TCE in the Fe^0 column effluent were below the detection limit. However, the concentrations of MCB and TCE in the final calcite column exceeded the maximum contaminant level （MCL） under the Safe Drinking Water Act of the US Environmental Protection Agency （US EPA） that protects human health and environment. These results suggested that partitioning of MCB and TCE into the gas phase could occur, and also that transportation of volatile organic pollutants in the gas phase was important. Three main precipitates formed in the ORC-GAC-Fe^0-CaCO3 system： CaCO3 in the ORC column along with Fe（OH）2 and FeCO3 in the Fe^0 column. The total porosity losses caused by mineral precipitation corresponded to about 0.24% porosity in the ORC column, and 1% in the Fe^0 column. The most important cause of porosity losses was anaerobic corrosion of iron. The porosity losses caused by gas because of the production and entrapment of oxygen in the ORC column and hydrogen in the Fe^0 column should not be ignored. Volatilization, precipitation and porosity losses were considered to be the main drawbacks of the ORC-GAC-Fe^0-CaCO3 system in remediating the MCB and TCE-contaminated aquifers. Thus, measurements such as using a suitable oxygen-releasing compound, weakening the increase in pH using a buffer material such as soil, stimulating biodegradation rates and minimizing the plugging caused by the relatively high dissolved oxygen levels should be taken to eliminate the drawbacks and to improve the efficiency of the ORC-GAC-Fe^0-CaCO3 system.     

Effect of soil application of cadmium contaminated lime on soil cadmium distribution and cadmium concentration in strawberry leaves and fruit

Heavy metal environmental pollution which occurs as a result of lime contaminated with cadmium (Cd) poses a potential health hazard. This investigation was undertaken to study uptake of Cd by strawberry plants grown in soil amended with three different sources and two different rates of industry waste lime containing 3.4, 14.3, and 60.0 mg Cd/kg, respectively. The effects of Cd applied to the soil were investigated, including its distribution in the soil and effect on Cd concentration in strawberry cv. Senga Sengana (Fragaria anassa) leaves and fruit in response to soil organic matter content and lime rates. Cadmium accumulated mainly in the plough layer, increasing from 0.170 mg Cd/kg (background level) to a maximum of 1.2 mg Cd/kg. Fruit had very high, hazardous Cd concentrations regardless of its content in the soil. This indicates that Cd was easily taken up by strawberry plants and accumulated in upper plant parts, including the fruit. Soil Cd content had no effect on concentration of this element in strawberry fruit. However, plant Cd uptake and fruit concentration was increased in acid soils even when soil Cd concentration was low.     

Influence of organic matter and pH on bentazone sorption in soils

Bentazone (3-isopropyl-1H-2,1,3-benzonthiadiazain-(4)3H-one 2,2-dioxide) is a postemergence herbicide which is used extensively worldwide, especially in China. The sorption of bentazone in various types of soils and extracted humic acids was investigated using a batch equilibration technique. Significant linearity was observed in sorption isotherms in five different types of soil, with distribution coefficients (K(d)) that varied between 0.140 and 0.321 mL g(-1). The distribution coefficient was determined to be a function of organic matter and pH in the soil. A model based on distribution coefficients was developed to predict bentazone sorption in soils. The organic matter-normalized partition coefficients for the neutral and anionic forms of bentazone were 370.3 and 2.40 mL g(-1), respectively. Hence, more attention should be given to the potential leaching problem when bentazone is applied in soils containing low organic matter and high pH.     

pH对土壤重金属吸附动力学的影响

The pH effect on the sorption kinetics of heavy metals in soils was studied using a constant flow leaching method. The soil samples were red soil collected from Yingtan, Jiangxi, and yellow-brown soil from Nanjing, Jiangsu. The heavy metals tested were zinc and cadmium. Assuming that the experimental data fitted to the following kinetic rate equation: 1/c·dx/dt = kx_∞-kx, the rate constant k of sorption could be determined from the slope of the straight line by plotting of 1/c·dx/dt vs. x. The results showed that the pH effect on the rate constants of heavy mental sorption in soils was very significant. The values of k decreased with increasing pH. The sorptions were more sensitive to pH in red soil than in yellow-brown soil.     

Cadmium soil sorption at low concentrations: I. Effect of time,cadmium load,pH, and calcium

Sorption of Cd at low concentrations onto two Danish soils (loamy sand, sandy loam) was examined in terms of kinetics and governing factors. From an environmental point of view soil sorption of Cd is a fast process: More than 95% of the sorption takes place within 10 min, equilibrium is reached in 1 hr, and exposures up to 67 wk did not reveal any long term changes in Cd sorption capacities. The soils have very high affinity for Cd at pH = 6.00 (10^?3 M CaCl₂) exhibiting distribution coefficients in the order of 200 to 250 (soil Cd concentration/solute Cd concentration). However, the sorption isotherms describing the distribution of Cd between soil and solute are slightly curvelinear. In the pH-interval 4 to 7.7, the sorption capacity of the soil approximately increases 3 times for a pH increase of one unit. Increasing the Ca concentration from 10^?3 to 10^?2 M reduces the sorption capacity of the sandy loam to one third.     

Specific sorption of trace amounts of cadmium by soils

Abstract

Sorption of trace quantities of Cd in four soils of different chemical and mineralogical properties, was studied. Initial Cd concentrations were between 15 to 150 μg. 1^?1. The sorption isotherms were linear and had a positive intercept in three of the soils, indicating a constant partition‐high affinity sorption isotherm (Giles et. al⁶). The data also followed the Freundlich sorption isotherm, and the Freundlich K parameter was taken as a measure of the relative affinity of the different soils for the Cd metal sorbed. Cadmium sorbed was extracted by IN‐NH₄C1 followed by 0.1N HC1, and the fraction remaining in the soils was considered specifically sorbed Cd. This fraction also followed a linear sorption isotherm, and was around 30% for the four soils studied. The sorption order for the amount of specifically sorbed Cd showed that the Boomer soil (kaolinite‐iron oxides) had the lowest affinity for specific sorption of this metal. This was taken as evidence that kaolinite and iron oxides have a lower capacity for retaining cadmium through specific sorption mechanism(s) than the materials present on the other soils (2:1 layer silicates and humic substances). The existence of specific mecha‐nism(s) responsible by the sorption of trace quantities of Cd in soil solutions has important implications on soil‐plant relationships, Cd mobility in soil profiles and control of Cd activity in soil solutions.     

Modelling the effects of pH on phosphate sorption by soils

Samples of six soils were incubated at 60°C for 24 h with several levels of either calcium carbonate or hydrochloric acid. Phosphate sorption was then measured on sub-samples of the treated soils over 24 h at 25°C. In one set of measurements on all soils, 0.01 M calcium chloride was used as the background electrolyte. In another set, on two soils, 0.01 M sodium chloride was used. An interpolation method was used to give points on the three-dimensional surface relating the final pH of the suspensions to sorption of phosphate at specified solution concentrations of phosphate. The effects of pH on phosphate sorption differed between soils. For unfertilized soils, increases in pH up to about pH 5.5 decreased sorption. Further increases in pH decreased sorption further in one soil and increased it in three others. For fertilized soils, measured sorption increased with pH. When sodium chloride was used instead of calcium chloride, there was a more marked trend for sorption to decrease as pH increased. Differences between the soils were ascribed to differences in two soil properties. One was the rate at which the electrostatic potential in the plane of adsorption decreased as pH increased. Only small differences in the rate of change of potential were needed to reproduce the observed differences between soils. The electrostatic potential would decrease more quickly in solutions of a sodium salt than in solutions of a calcium salt and this explains the observed differences between these media. The other soil property that affected observed sorption was the release of phosphate from the soil. The amount released was largest at low pH. Consequently, for fertilized soils, measured sorption increased with pH.     

长江三角洲地区典型土壤对铅的吸附及其与有机质、pH和温度的关系

采用批平衡方法实验研究了长江三角洲地区4种典型土壤对Pb的吸附、解吸行为及有机质和温度对Pb吸附的影响,并运用热力学参数K°、ΔG°、ΔH°和ΔS°解释了土壤Pb的吸附机理。结果表明,在本实验条件下,Pb在土壤上的吸附过程表现出明显的非线性,符合Freundlich模型。土壤Pb吸附Kf值大小为:滩潮土(石质淡色潮湿雏形土)(3816dm3kg-1)>乌黄土(底潜铁聚水耕人为土)(1984dm3kg-1)>青紫泥(普通潜育水耕人为土)(1030dm3kg-1)>黄泥砂土(铁聚潜育水耕人为土)(348dm3kg-1)。去除有机质后的土壤对Pb的吸附量降低,解吸率升高。吸附反应热力学表明,K°和ΔS°随温度升高而增大,ΔG°随温度升高而降低。ΔG°为负值,表明Pb吸附反应为自发反应,ΔH°为正值表明土壤Pb吸附为吸热反应。乌黄土、青紫泥和滩潮土对铅吸附的主要作用力为化学键力,黄泥砂土为范德华力和偶极间力。Pb在土壤上的解吸过程存在明显的滞后现象。pH、碳酸钙含量和平衡浓度越高,滞后系数越大,这可能与在高pH和高碳酸钙含量时,Pb与土壤形成难解吸内圈配位物有关。     

石灰用量对酸性土壤pH值及有效养分含量的影响

采用室内培养法,设置不施生石灰和生石灰用量0.3、0.9、1.8、2.4、4.8 g/kg,共6个用量梯度,研究不同生石灰用量对酸性土壤pH值动态变化、有效养分含量的影响及土壤pH值与有效养分含量之间的相关性。结果表明,生石灰的施入,可以显著提高土壤pH值,改善土壤酸度。培养到第90 d,生石灰用量4.8、2.4、1.8g/kg处理较对照分别提高了2.88、1.16和0.74个pH单位。施用生石灰对土壤全氮含量影响不大,但对土壤无机氮影响显著。生石灰用量在0~2.4 g/kg范围内,土壤硝态氮含量随生石灰用量的增加而显著增加,增幅为12.4%~146.8%,当生石灰用量2.4 g/kg时,土壤硝态氮含量显著降低。土壤铵态氮的变化趋势则刚好相反,随着生石灰用量的增加而减少;土壤有效磷含量随着生石灰用量的增加先升高后降低;对于土壤速效钾来说,当生石灰用量0.9 g/kg,其含量随着石灰用量的增加而显著降低,降幅为2.9%~21.7%。施用生石灰可以显著提高土壤有效Ca含量,且随生石灰用量的增加而显著增加,增幅为32.3%~543.0%。生石灰的施用显著降低了土壤有效Fe、Mn、Cu、Zn的含量,且当生石灰用量≥2.4 g/kg时,土壤有效Mn、Zn含量均已处于极其缺乏的状况。土壤pH值与土壤全氮、铵态氮、速效钾、有效Fe、Mn、Cu、Zn呈显著线性负相关,与有效Ca呈极显著线性正相关,与土壤硝态氮、有效磷和有效Mg则符合二次函数,各相关系数均达到极显著水平。土壤养分与土壤酸度有着较好的相关性,在施用石灰改良酸性土壤时,要特别注意其施用量及土壤有效Mn、Zn等微量元素的及时补充。     

Competitive sorption of cadmium and lead in acid soils of Central Spain

The bioavailability and ultimate fate of heavy metals in the environment are controlled by chemical sorption. To assess competitive sorption of Pb and Cd, batch equilibrium experiments (generating sorption isotherms) and kinetics sorption studies were performed using single and binary metal solutions in surface samples of four soils from central Spain. For comparisons between soils, as well as, single and binary metal solutions, soil chemical processes were characterized using the Langmuir equation, ionic strength, and an empirical power function for kinetic sorption. In addition, soil pH and clay mineralogy were used to explain observed sorption processes. Sorption isotherms were well described by the Langmuir equation and the sorption kinetics were well described by an empirical power function within the reaction times in this study. Soils with higher pH and clay content (characterized by having smectite) had the greatest sorption capacity as estimated by the maximum sorption parameter (Q) of the Langmuir equation. All soils exhibited greater sorption capacity for Pb than Cd and the presence of both metals reduced the tendency for either to be sorbed although Cd sorption was affected to a greater extent than that of Pb. The Langmuir binding strength parameter (k) was always greater for Pb than for Cd. However, these k values tended to increase as a result of the simultaneous presence of both metals that may indicate competition for sorption sites promoting the retention of both metals on more specific sorption sites. The kinetic experiments showed that Pb sorption is initially faster than Cd sorption from both single and binary solutions although the simultaneous presence of both metals affected the sorption of Cd at short times while only a minor effect was observed on Pb. The estimated exponents of the kinetic function were in all cases smaller for Pb than for Cd, likely due to diffusion processes into micropores or interlayer space of the clay minerals which occurs more readily for Cd than Pb. Finally, the overall sorption processes of Pb and Cd in the smectitic soil with the highest sorption capacity of the studied soils are slower than in the rest of the soils with a clay mineralogy dominated by kaolinite and illite, exhibiting these soils similar sorption rates. These results demonstrate a significant interaction between Pb and Cd sorption when both metals are present that depends on important soil properties such as the clay mineralogy.     

不同氮磷钾肥对土壤pH和镉有效性的影响

采用土壤培养方法研究了不同氮、磷、钾肥对土壤pH和镉有效性的影响。结果表明,在培养60 d时,所有氮肥处理均降低了土壤pH,增加了Cd的提取量;但高量尿素和氯化铵处理土壤pH降低最多,提取的Cd也最多;硫酸铵提取的Cd较对照增加最小。所有磷肥处理均引起土壤pH小幅降低,但对土壤Cd提取量的影响以普钙稍大。3种钾肥处理均降低了土壤pH,其中氯化钾在0 d时提取的Cd在所有钾肥处理中为最高,其提取能力15 d后逐渐消失,试验结束时所有钾肥处理对Cd提取量均低于对照。本研究进一步表明,在土壤Cd含量处于污染临界值附近或已受Cd污染的土壤上,应避免施用高量的酸性肥料如尿素、氯化铵、普钙,以及其他酸性物料。在常用磷、钾肥中,磷酸二铵和硫酸钾在Cd污染土壤上施用更为适合。     

太湖流域典型水稻土对镉吸持特征的初步研究

研究了太湖流域两种典型水稻土黄泥土和板浆白土对镉的吸附和解吸及其pH的影响.发现黄泥土吸附百分数较板浆白土大,而解吸百分数较小,镉吸附前后两个土壤的pH值均有明显差异.     

Effects of soil organic matter on pH-dependent phosphate sorption by soils

Effects of soil organic matter (80M) on P sorption of soils still remain to be clarified because contradictory results have been reported in the literature. In the present study, pH-dependent P sorption on an allophanic Andisol and an alluvial soil was compared with that on hydrogen peroxide (H₂0₂)-treated, acid-oxalate (OX)-treated, and dithionite-citrate- bicarbonate (DCB)-treated soils. Removal of 80M increased or decreased P sorption depending on the equilibrium pH values and soil types. In the H₂O₂ OX-, and DCB-treated soils, P sorption was pH-dependent, but this trend was not conspicuous in the untreated soils. It is likely that 80M affects P sorption of soils through three factors, competitive sorption, inhibition of polymerization and crystallization of metals such as AI and Fe, and flexible structure of metal-80M complexes. As a result, the number of available sites for P sorption would remain relatively constant in the wide range of equilibrium pH values in the presence of 80M. The P sorption characteristics were analyzed at constant equilibrium pH values (4.0 to 7.0) using the Langmuir equation as a local isotherm. The maximum number of available sites for P sorption (Q _max) was pH-dependent in the H₂0₂-, OX-, and DCBtreated soils, while this trend was not conspicuous in the untreated soils. Affinity constants related to binding strength (K) were less affected by the equilibrium pH values, soil types, and soil treatments, and were almost constant (log K ≈ 4.5). These findings support the hypothesis that 80M plays a role in keeping the number of available sites for P sorption relatively constant but does not affect the P sorption affinity. By estimating the Q _max and K values as a function of equilibrium pH values, pH-dependent P sorption was well simulated with four or two adjustable parameters. This empirical model could be useful and convenient for a rough estimation of the pH-dependent P sorption of soils.     

Effect of pH on chemical forms and plant availability of cadmium,zinc, and lead in polluted soils

The effect of pH on chemical forms and plant availability of heavy metals in three polluted soils was investigated. The soils were adjusted to pH values of 7.0, 6.0, and 4.5, then sequentially extracted so that Cd, Zn, and Pb could be partitioned into five operationally defined chemical fractions: exchangeable, carbonate, Fe-Mn oxide, organic, and residual. Kidney beans were grown in the soils to investigate plant availability of the metals in relation to changes of their levels in chemical forms resulting from alteration of soil pH. Alteration of pH resulted in changes of chemical forms of the metals in the soils, and at lower pH the changes were more significant. When soil pH values were decreased from 7.0 to 4.55, levels of Cd, Zn, and Pb in exchangeable form increased, decreased in carbonates and decreased slightly in Fe-Mn oxide forms. Their levels in organic and residual forms were unchanged. Although concentration of metals in plants increased with reduction in soil pH values, dry matter yields were also restricted, so that the amount of metal uptake were almost similar. The uptake rate of the metals in the exchangeable + carbonate forms was the same for the three elements in all the cases.     

Effect of manganese and soil pH on the iron content of crops grown on podzol soils

In a greenhouse study on three podzol soils with pH values of 5.4–5.6, liming to pH 7.6 or higher decreased the Fe concentration of pea plant tissues from 47 to 42 ppm. In the case of barley, liming the soil increased the mean tissue Fe concentration from 104 to 119 ppm at pH 7.6 and to 107 ppm at pH 7.7. Field experiments on wheat, oats, alfalfa, and timothy showed that Mn applied to the soil or as foliar spray did not affect the Fe concentration of cereal or forage plant tissues. Liming did not affect the Fe concentration of cereal kernels but on a few locations it increased the Fe concentration of the boot stage tissue. The Fe concentration in oats was higher than that in wheat. Based on the results of a survey, it was found that forage legumes contained more Fe than did timothy. The survey also showed that a few Fe values in timothy and cereals would be considered low, although Fe deficiency has not been experienced in this region. A number of the samples would be in the deficiency range from the animal nutrition standpoint.