pH Effect on kinetics of Heavy Metal Sorption in Soils

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,Jiansu,The heavy metals tested were zinc and cadmium.Assuming that the experimental data diffed 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.     

七种钾释放动力学方程的比较和动力学参数的应用

Batch equilibrium experiments were conducted to investigate cadmium （Cd） sorption by two permanent-charge soils, a yellow-cinnamon soil and a yellow-brown soil, and two variable-charge soils, a red soil and a latosol, with addition of selected organic acids （acetate, tartrate, and citrate）. Results showed that with an increase in acetate concentrations from 0 to 3.0 mmol L^-1, Cd sorption percentage by the yellow-cinnamon soil, the yellow-brown soil, and the latosol decreased. The sorption percentage of Cd by the yellow-clnnamon soil and generally the yellow-brown soil （permanent-charge soils） decreased with an increase in tartrate concentration, but increased at low tartrate concentrations for the red soil and the latosol. Curves of percentage of Cd sorption for citrate were similar to those for tartrate. For the variable-charge soils with tartrate and citrate, there were obvious peaks in Cd sorption percentage. These peaks, where organic acids had maximum influence, changed with soil type, and were at a higher organic acid concentration for the variable-charge soils than for the permanent charge soils. Addition of cadmium after tartrate adsorption resulted in higher sorption increase for the varlable-charge soils than permanent-charge soils. When tartrate and Cd solution were added together, sorption of Cd decreased with tartrate concentration for the yellow-brown soil, but increased at low tartrate concentrations and then decreased with tartrate concentration for the red soil and the latosol.     

施入粉煤灰和污泥对酸性淋溶土镉和铅吸附的影响

The safe recycling of fly ash (FA) and sewage sludge (SS) in the agricultural processes comprises an important environmental technology on waste management. Soils amended with FA and SS may change their ability to adsorb heavy metals due to either increase of soil pH or decomposition of sludge-borne organic matter. Thus, Cd and Pb sorption was investigated by 1-month incubation under soil moisture content at field capacity and room temperature with an acidic Typic Haploxeroalf from central Greece amended with varying amounts of FA and SS. Batch experiments were conducted by equilibrating the soil samples with CaCl₂ solutions containing 0-400 mg Pb L^-1 or 0-100 mg Cd L^-1. The results showed that the Freundlich equation described well the Cd and Pb sorption. Distribution coefficient (K_d) values of Pb were higher than those of Cd in all the treatments of this study. Application of FA increased K_d values for Cd and Pb to 8.2 and 2.3 times more than the controls, respectively. Simultaneous applications of FA and SS caused a K_d increase of 3.8 and 2.1 times compared to the treatments that received only SS for Cd and Pb, respectively. Treatment of SS alone did not significantly change Cd and Pb sorption compared to the controls. The sorption reactions seemed to be mainly affected by soil pH, which was revealed by the significant correlations of Cd and Pb sorption with soil pH. These suggested that fly ash was very useful as a low-cost adsorbent for Cd and Pb and could be used as an ameliorant for biosolid-amended acidic soils.     

华中地区旱地氮素矿化的能力

Nitrogen mineralization potentials of 15 soil samples were studied by the methods of soil aerobic incubation, and the correlation between the potentials and the amounts of nitrogen taken up by rye grass (Lolium multiflorum Lam.) in pot culture was calculated. The soils were collected from Hubei Province in Central China. Soil nitrogen mineralization potentials (N_O) were calculated and optimized by a quick-BASIC program. N_O ranged from 60 mg kg^-1 to 340 mg kg^-1, which accounted for 9.1% to 34.6% of the total nitrogen content. Among the examined soils, yellow-brown soil collected from Wuhan had the largest N_O and brown-red soil from Xianning had the smallest one. The mineralization rate constants (k) ranged from 0.00556 d^-1 to 0.01280 d^-1, in average 0.00882 d^-1. Chao soil from Wuhan had the greatest k while yellow-cinnamon soil from Zhaoyang had the smallest one. There were apparent differences between mineralization parameters (N_O and k) optimized and non-optimized ones. Optimized N_O had a better correlation than non-optimized N_O with the amount of nitrogen accumulated in the aerial parts of rye grass. N_O, N_O × k and N_t(accumulated mineralized nitrogen within time t) could be used as indexes of soil nitrogen supply. Among them N_t was the best, which was significantly correlated with the amounts of nitrogen accumulated in the aerial parts of rye grass harvested at three different times.     

钙盐诱导下土壤锰和铁的释放及其对胡椒的生物有效性

Releases of manganese and iron ions from an albic soil (Albic-Udic Luvisol), a yellow-red soil (Hap-Udic Ferrisol) and a yellow-brown soil (Arp-Udic Luvisol) induced by calcium salt addition and their bioavailability to pepper (Capsicum frutescens L.) were studied in a pot experiment. Addition of Ca(NO₃)₂ decreased soil pH and increased both exchangeable and DTPA (diethylenetriamine pentaacetic acid)-extractable Mn and Fe in soils. Meanwhile, total Mn accumulation in the shoots of Capsicum frutescens L. on the salt-treated soils increased significantly (P< 0.01) compared with the control, suggesting that salt addition to soil induced Mn toxicity in Capsicum frutescens L. Although exchangeable and DTPA-extractable Fe increased also in the salt-treated soils, Fe uptake by the shoots of Capsicum frutescens L. decreased. The effect of added salts in soils on dry matter weight of pepper varied with the soil characteristics, showing different buffer capacities of the soils for salt toxicity in an order of yellow-brown soil > albic soil > yellow-red soil. Fe/Mn ratio in shoots of Capsicum frutescens L. decreased with increasing salt addition for all the soils, which was ascribed to the antagonistic effect of Mn on Fe accumulation. The ratio of Fe/Mn in the tissue was a better indicator of the appearance of Mn toxicity symptoms than Mn concentration alone.     

苏南地区土壤重金属向蔬菜的迁移研究

Vegetable fields in peri-urban areas receive large amounts of extraneous heavy metals because of rapid urbanization and industrialization in China. The concentrations of Cu, Zn, and Pb in 30 soil samples and 32 vegetable samples, collected from 30 different sites in southern Jiangsu Province of China, were measured and their transfer from soil to vegetable was determined. The results showed that the soil samples had wide ranges of pH (4.25-7.85) and electrical conductivity (EC) (0.24-3.42 dS m^-1). Among the soil samples, there were four soil samples containing higher Cu and two soil samples containing higher Zn concentrations than those specified in the Chinese Soil Environmental Quality Standard II. However, no vegetable sample was found to contain a high level of Cu or Zn. In contrast, one vegetable sample contained 0.243 mg Pb kg^-1 FW, which was above the Chinese Food Hygiene Standard, whereas the corresponding soil Pb concentration was lower than the Chinese Soil Environmental Quality Standard II. The transfer coefficients of Cu of all vegetable samples exceeded the suggested coefficient range, implying that extraneous Cu had high mobility and bioavailability to vegetables. There was no significant correlation between extractable soil heavy metal concentrations with four kinds of extractants and soil pH, EC, heavy metal concentrations in vegetables and soils, except that soil pH correlated well with the extractable soil Cu, Zn, and Pb concentrations with 1.0 mol L^-1 NH₄NO₃. Moreover, diethylenetriamine pentaacetic acid (DTPA) extraction method was a more effcient method of extracting heavy metals from the soils independent of soil pH and EC than other three methods used.     

红壤重金属的复合污染

The effects of combined heavy metal pollution of red soil on the growth of wetland rice and the transfer of Pb,Cd,Cu and Zn from soil into plants were sudied by greenhouse pot experiment,The results showed that the plantyields were markedly affected by heavy metals,with the exception of Pb,in soils under the experimental conditions,without taking into consideration all the interactions among the elements.The concentrations of the elemets in plants were mainly affected by the specific element added to the soil.The effect of interactions among the heavy metals was very significant either on plant yields or on the concentration of the elements in plants.The risk assessment of a combined pollution by heavy metals in the soil is discussed preliminarily in terms of the relative pollution equivalent.     

陇海铁路郑州—圃田段铁路旁土壤重金属污染

The pollution status and horizontal distribution of heavy metals (Ni, Pb, Cr, Zn, Cu, and Cd) in the soil on railroad side along the Zhengzhou-Putian section of Longxi-Haizhou Railroad were studied by collecting soil samples along a sampling section perpendicular to the railroad at the distances of 0, 10, 20, 30, 50, 100, 200, 300, and 500 m from the railroad edge. The concentrations of heavy metals in the sampling soils were higher than those of the control site. The concentrations of Pb, Zn, and Cd were found to be the highest in the soils at the railroad edge, and then decreased with increasing distance from the railroad. The highest concentrations of Ni, Cr, and Cu in soils were located at about 10-30 m from the railroad. Compared with the single factor pollution index (SFPI) of heavy metals calculated for the control site, the average SFPI from the sampling sites decreased in the order of Cr > Cd > Pb > Zn > Ni > Cu. There were notable negative correlations between the integral pollution index (IPI) of soil heavy metals at all sampling sites and the distances from the railroad. According to three IPIs calculated from the background values of heavy metals in och-aquic Cambisols, the heavy metal concentrations in the control soil, and the 2nd levels for soil heavy metals in GB15618-1995, the study area could be divided, based on the distances from the railroad, into four pollution zones: heavy pollution zone (0-10 m), medium pollution zone (10-50 m), slight pollution zone (50-100 m), and warning zone (100-500 m), respectively.     

中国东部太湖地区酸性水稻土团聚体上铜的专性和非专性吸附动力学研究

The Taihu Lake region in East China has become prone to soil acidification, which changes heavy metals such as copper(Cu) in soil into water-soluble species and increases the mobility and contamination risks of heavy metals in the biological environment. In this study, the kinetics of Cu2+sorption by the bulk soil and the aggregate size fractions of an acidic paddy soil collected from the Taihu Lake region, the effects of temperature on Cu2+sorption, and the p H changes of the solution were investigated by static sorption and magnetic stirring. The aggregate size fractions were prepared by low-energy ultrasonic dispersing and freeze-drying. The total sorption amounts of the bulk soil and the aggregate size fractions for Cu2+followed a descending order of clay > coarse sand > bulk soil > silt> sand, corresponding to those of organic matter content, free iron oxide content, free aluminum oxide content, and cation exchange capacity. The kinetic sorption curves of Cu2+by the bulk soil and the aggregates, which were divided into two stages(rapid and slow sequentially), were well fitted by the first-order equation, the diffusion equation, and the Elovich equation, showing significant correlations(P < 0.05). Specific and non-specific sorption dominated in the fast and slow stages, respectively, and the former was predominant throughout the sorption process. The specific sorption accelerated and the non-specific sorption decelerated with rising temperature. The p H of the solution decreased significantly during the specific sorption and remained unchanged or increased slightly during the non-specific sorption. When the specific sorption terminated, the p H of the solution was minimized nearly simultaneously.The sorption progress of Cu2+by the bulk soil significantly preceded that by the aggregates. Therefore, heavy metal contamination may be another factor reducing soil p H and metal sorption forms should be taken into consideration in studies of mitigating soil heavy metal pollution or determining environmental capacity of heavy metal in soil.     

较贫瘠的红壤中有机质的积累及其生态意义

Field experiments on the decomposition of organic materials and the accumulation of organic carbon in infertile red soils were conducted at the Ecological Experimental Station of Red Soil, the Chinese Academy of Sciences, and the potential of CO₂ sequestration by reclamation and improving the fertility of these soils was estimated. Results showed that in infertile red soils, the humification coefficients of organic materials were rather high, ranging from 0.28 to 0.63 with an average of 0.43, which was 41% higher than those in corresponding red soils with medium fertility. This was mainly attributed to the high clay content, high acidity and low native organic matter content of infertile red soils. Compared to those in corresponding normal red soils, the decomposition rates of organic materials were significantly lower in infertile red soils in the first 2 years, thereafter no significant difference was observed between those in the two kinds of soils. Depending on the kind and amount of organic manure applied, the soil properties and the rotation systems, annual application of organic manure with a rate of 4 500 to 9 000 kg ha^-1 increased the organic carbon content in surface 20 cm of infertile red soils by 2.1~7.5 g kg^-1 with an average of 4.7 g kg^-1 within the first 5 years. The organic carbon content in infertile red soils which received organic manure annually increased linearly in the first 10 years, thereafter it slowed down, implying that the fertility of the infertile red soils could reach middle or high level in 10 years if the soil was managed properly. It was estimated that through exploitation of wastelands, re-establishment of fuel forests and improvement of soil fertility, soils in red soil region of China could sequester an extra 1.50 × 10¹⁵ g of atmospheric CO₂.     

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.     

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.     

Response of the sorption behavior of Cu,Cd, and Zn to different soil management

This study investigated the effect of different farming practices over long time periods on the sorption‐desorption behavior of Cu, Cd, and Zn in soils. Various amendments in a long‐term field experiment over 44 y altered the chemical and physical properties of the soil. Adsorption isotherms obtained from batch sorption experiments with Cu, Cd, and Zn were well described by Freundlich equations for adsorption and desorption. The data showed that Cu was adsorbed in high amounts, followed by Zn and Cd. In most treatments, Cd ions were more weakly sorbed than Cu or Zn. Generally, adsorption coefficients K_F increased among the investigated farming practices in the following order: sewage sludge ≤ fallow < inorganic fertilizer without N ≈ green manure < peat < Ca(NO₃)₂ < animal manure ≤ grassland/extensive pasture. The impact of different soil management on the sorption properties of agricultural soils for trace metals was quantified. Results demonstrated that the soil pH was the main factor controlling the behavior of heavy metals in soil altered through management. Furthermore, the constants K_F and n of isotherms obtained from the experiments significantly correlated with the amount of solid and water‐soluble organic carbon (WSOC) in the soils. Higher soil pH and higher contents of soil organic carbon led to higher adsorption. Carboxyl and carbonyl groups as well as WSOC significantly influenced the sorption behavior of heavy metals in soils with similar mineral soil constituents.     

The Influence of Organic Carbon and pH on Heavy Metals,Potassium, and Magnesium Levels in Lithuanian Podzols

Industrial activities can contribute to the accumulation of heavy metals in soils, which could potentially threaten public health and the environment. This research was conducted to investigate the relationships between pH and total organic carbon (TOC) with soil chemical parameters, including exchangeable and total Cu, Zn, Cd, Pb, K, and Mg concentrations in soils near Panevėžys and Kaunas, Lithuania. Principal component regression (PCR) and non‐linear regression were used to find statistical relationships between pH, TOC, and the other soil properties studied. The results of correlation tests indicated that pH and TOC had strong relationships with most of the soil properties. The results of PCR [R ² = 0·87, RMSE = 0·046] and non‐linear regression [R ² = 0·91, RMSE = 0·041] (pH and the entire parameters), PCR [R ² = 0·777, RMSE = 0·058] and non‐linear regression [R ² = 0·871, RMSE = 0·046] (pH and the exchangeable parameters) to model the relationships between pH and soil chemical properties were promising and significant. Exchangeable heavy metal concentrations increased for pH > 5. Even though the relationships between TOC and heavy metals were significant, they were not as powerful as the relationships between pH and these metals. It was concluded that total metal concentrations in the study soils can be predicted by either pH or TOC. Metal mobility could most likely be controlled at the study site by manipulating soil pH and/or TOC. Finally, it is suggested that when there are financial and time limitations, assessment of total exchangeable metal concentrations using soil pH and/or TOC could be productive. Copyright © 2016 John Wiley & Sons, Ltd.     

石灰和双氰胺对红壤酸化和硝化作用的影响及其机制

施用石灰是改良酸性土壤的重要措施,但其对土壤硝化作用的增强不仅加速土壤酸化,也增加硝态氮流失风险.传统的硝化抑制剂双氰胺(Dicyandiamide,DCD)能否在石灰改变pH的条件下始终有效抑制硝化是当前红壤区生产中亟需解决的问题.采用短期土壤培养试验,探讨了不同用量石灰与DCD配合施用对土壤酸化和硝化作用的影响及其...     

几种土壤剖面的硝化作用及其动力学特征

选用陕西省六种主要耕作土壤及其剖面不同层次23个土样,在实验室培养条件下,研究其硝化作用的特点,并选用dN/dt=bN(B-N)/B方程（式中,N为硝态氮的累积量,t为试验培养时间,B耿硝态氮累积量的渐进值）,描述硝化作用过程中硝态氮含量随时间的累积,获得定量描述硝化作用强弱的两个指标（Kmx和td)。结果表明耕层土壤由北向南硝化作用强度逐渐减弱,硝化作用的最大速率（Kmx)变幅为2．70－16．58mg/kg.d,陕北的黑垆硝化作用进行最快,陕南的黄泥巴最慢,在不同土壤剖面中,硝化作用由上到下呈现减弱趋势,硝化作用的最大速率（Kmx)随土层深度增加而下降,迟缓期（td)随土层深度增加而延长,在粘化层和粘重土层中,硝化作用非常微弱或基本不发生硝化作用,这些不同土壤及剖面层次硝化作用的较差与土壤的物理,化学特性有关。     

土壤吸附砷酸盐动力学的初步研究

本研究目的是了解陕西省的几种土壤吸附和解吸附砷酸盐的速率和过程,以及其吸附能量。Kuo和Lotse导出的双常数速率公式拟合试验资料优于一级、二级、三级反应公式,抛物线扩散和Elovich公式等五个公式。用双常数速率公式(C=k·C₀·t^1/m)分两段拟合能进一步提高拟合优度。根据Arrhenius公式计算出的吸附活化能是0.70—3.40千卡/克分子。低的活化能表明,供试土壤对砷酸盐的吸附作用是一种完全不同于真溶液条件化学反应的物理学过程。土壤吸附和解吸附砷酸盐的速度和容量受作用时间、温度、溶液∶土壤比率,加入的砷量和浓度,以及土壤特性的影响。粘土的吸附反应常数(k),吸附量比沙壤土大。而沙壤土有高的解吸附反应速度常数(k_-1^'),砷酸盐容易被解吸附而释放出来。     

土壤对磷的吸持特性及其与土壤供磷指标之间的关系

本试验测定了浙江省几种代表性土壤对磷的等温吸持特性。实测值与Frundlich、Langmuir、两项式Langmuir和Temkin方程都很符合,相关系数变化范围在0.919-0.999之间,都达到极显著水平。其中以简单Langmuir等温式与本实验资料最为吻合。从Langmuir方程得到的土壤吸持特性值(k×q_m)被认为与土壤供磷特性有关。几种供试样品的(k×q_m)值是:针铁矿21100>黄筋泥4218>黄筋泥田991>青紫泥798>粉泥田660>高岭石485>老黄筋泥田423>泥质田298。根据土壤吸持特性值以田菁进行盆栽试验来估算作物磷肥需要量,结果表明,供磷强度0.3ppm P基本能满足田菁早期生长的需要。为使不同土壤达到相同的供磷强度,(k×q_m)值大的土壤要求更高的有效磷值。供试土壤的几种磷素指标:E值、Bray1-P值和(NaOH-Na₂C₂O₄)法值对(k×q_m)值的变化比较敏感,而EDTA-P和Olsen-P指标对(k×q_m)值的变化较为迟钝。     

Immobilization of the heavy metals Cd, Cu and Pb in an acid soil amended with gypsum- and lime-rich industrial by-products

In situ stabilization of heavy metals in contaminated soils by the addition of various types of soil amendment is an attractive technique for remediation. We investigated the potential of three industrial by‐products (phosphogypsum, red gypsum and dolomitic residue) for boosting the heavy metal sorption capacity of an acid soil (patents pending, Spanish applications no 200201704 and 200201375) by using sorption isotherm experiments. The three by‐products were found substantially to increase the retention of lead, cadmium and copper on the solid components of the soil. The increase in lead retention of the soil horizons upon the addition of both phosphogypsum and red gypsum was dominated by the formation of anglesite minerals. The dolomitic residue increased the metal retention capacity of the soil horizons through the precipitation of laurionite‐type minerals as well as cadmium and copper hydroxy‐chlorides. In addition to the batch sorption study, we used scanning electron microscopy to investigate the metal sorption processes in the soil by the effect of the treatments. Lead was frequently found to be linked to the edge charges of kaolinite minerals. The three metals were found to be associated with organic matter in the Ap horizon treated with the three by‐products. Finally, the three metals were found to be associated with undissolved dolomitic residue particles.