A review of cadmium sorption mechanisms on soil mineral surfaces revealed from synchrotron-based X-ray absorption fine structure spectroscopy: Implications for soil remediation

The sorption of cadmium(Cd) is one of the most important chemical processes in soil, affecting its fate and mobility in both soil and water and ultimately controlling its bioavailability. In order to fundamentally understand the sorption/desorption of Cd in soil systems, X-ray absorption fine structure spectroscopy(XAFS) has been applied in numerous studies to provide molecular-level information that can be used to characterize the surface adsorption and precipitation reactions that Cd can undergo. This information greatly improves our current knowledge of the possible chemical reactions of Cd in soil. This paper critically reviews the mechanisms of Cd sorption/desorption at the mineral-water interface based on XAFS studies performed over the past twenty years. An introduction to the basic concepts of sorption processes is provided, followed by a detailed interpretation of XAFS theory and experimental data collection and processing,ending finally with a discussion of the atomic/molecular-scale Cd sorption mechanisms that occur at the soil mineral-water interface. Particular emphasis is placed on literature that discusses Cd adsorption and speciation when associated with iron, manganese, and aluminum oxides and aluminosilicate minerals.Multiple sorption mechanisms by which Cd is sorbed by these minerals have been found, spanning from outer-sphere to inner-sphere to surface precipitation,depending on mineral type, surface loading, and pH. In addition, the application of complementary techniques(e.g.,113 Cd nuclear magnetic resonance(NMR) and molecular dynamics simulation) for probing Cd sorption mechanisms is discussed. This review can help to develop appropriate strategies for the environmental remediation of Cd-contaminated soils.     

潮土条件下长期施肥对作物产量、氮吸收与土壤剖面中硝酸盐含量分布的影响

Soil properties were investigated in sites where three succeeding generations of Chinese fir (Cunninghamia lanceolata (Lambert) Hooker) in Nanping, Fujian, China, were cultivated in order to show the impact of a repeated monoculture on site productivity. Compared with the first generation (FG) stand the soil structure deteriorated in the second generation (SG) and the third generation (TG) stands. For instance, the destruction rate of the peds increased by 55%-115% in the SG and the TG stands compared to the FG stand. Soil nutrient storage and nutrient availability also decreased in the SG and the TG stands. For surface soils of 0-20 cm, the organic matter content, total N and P, and available N and P decreased by 3%-20% relative to those in the FG stand. For many soil parameters, the differences between the FG stand and the SG and the TG stands were statistically significant (LSD test, P < 0.05). Furthermore, with each succeeding generation of Chinese fir, the total number of soil microbes declined, the soil enzyme activity weakened, and the soil biological activity decreased. In order to maintain sustainable site productivity, new silvicultural practices need to be developed for management of Chinese fir plantations.     

一种模拟土壤养分提取及及植物吸收的装置研究

In situ evaluating the availability of soil nutrients has been a challenge. In this study, a new type of Device for Simulating Soil Nutrient Extraction and Plant Uptake (DSSNEPU) and its operating procedures were introduced. The device consists of a sampling tube, a fluid supply system, a low pressure system, a tube sheath and an elution cylinder. The sampling tube was firstly soaked in the solution of 0.5 mol L 1 NaHCO 3 and then buried into soils. The fluid supply system was connected to the sampling tube and the deionized water was supplied. During the period, low pressure system started a vacuum for 3 min every 10 min interval. After extraction, the sampling tube was removed and the nutrients on the sampling tube were eluted with 0.5 mol L 1 HCl. The elution solution was used for nutrient measurement. The amounts of P and K extracted by DSSNEPU reached the maximal values after 4 h. No significant increases of P and K were observed for longer extraction duration. The optimal temperature for extracting P and K was 30 C in this experiment. Extracted P and K were increased by 83.3% and 84.6% with the employment of low pressure system in comparison to those without employing low pressure system. Correlation analysis indicated that P and K extracted by DSSNEPU were highly correlated with those by conventional chemical extraction and by plant uptake. The above results suggest that this device is applicable to assess the availability of nutrients in soils.     

The effects of clay,organic matter and time on adsorption and plant uptake of cadmium added to the soil

In a 2-yr pot experiment the effects of texture and organic matter content on adsorption in soil and uptake in Perennial ryegrass (Lolium perenne) and Winter rape (Brassica napus) of Cd added to the soil were studied. The soils used were a clay, a loamy sand and a sapric peat mixed in different proportions. One mg kg^?1 of Cd was added to each soil mixture. The organic matter showed a greater ability than clay to adsorb Cd in an unavailable form and thereby reduce plant uptake. The effect per unit of organic matter added was greatest at low organic matter content. Most of the Cd was adsorbed in a non-exchangeable form indicating the presence of strong organic complexing. The addition of organic matter reduced plant uptake more efficiently in sand than in clay even though the exchangeable Cd did not differ between the two soils. Increasing the clay content in sand from 9 to 63% led to slightly decreased water leachability but did not significantly decrease non-exchangeable Cd. Neither was plant uptake notably affected. The two crops showed a similar reaction to the different treatments. Uptake was correlated with Cd extractable in ammonium acetate at pH 7, but the relationship was different at each sampling occasion. No significant change in adsorption of the added Cd, fixation, was detected during the 2-yr period but seasonal variations in solubility and uptake were noticed.     

Effect of zeolite application and soil pH on cadmium sorption in soils

Abstract

In this study the influence of zeolite application and soil liming on cadmium (Cd) sorption by soils in Greece was investigated. The zeolite was natural and consisted mainly of clinoptilolite. The soil samples were strongly acid surface horizons of an Alfisol limed from a pH of 4.0 to 8.5, and a neutral Bt horizon. The result showed that liming and zeolite application substantially increased sorption of Cd in the soils. Cadmium sorption was described adequately by the Freundlich equation whereas the Langmuir model failed to describe Cd sorption in the soils. The Freundlich constant K increased in value by zeolite application as well as by soil liming. A strong relationship was observed between this parameter and soil pH. A high percentage of cadmium sorbed was released in the desorption procedure. The amount of Cd released was reduced by zeolite application as well as by soil liming. It is concluded that zeolite application as well as soil liming increased Cd sorption by the soils.     

A mechanistic model for describing the sorption and desorption of phosphate by soil

A model of phosphate reaction is constructed and its output compared with observations for the sorption and desorption of phosphate by soil. The model has three components: first, the reaction between divalent phosphate ions and a variable-charge surface; second, the assumption that there is a range of values of surface properties and that these are normally distributed; third, the assumption that the initial adsorption induces a diffusion gradient towards the interior of the particle which begins a solid-state diffusion process. The model closely describes the effects on sorption of phosphate of: concentration of phosphate, pH, temperature, and time of contact. It also reproduces the effects on desorption of phosphate of: period of prior contact, period and temperature of desorption, and soil: solution ratio. The model is general and should apply to other specifically adsorbed anions and cations. It suggests that phosphate that has reacted with soil for a long period is not ‘fixed’ but has mostly penetrated into the soil particles. The phosphorus can be recovered slowly if a low enough surface activity is induced.     

Cadmium soil sorption at low concentrations: VI. A model for zinc competition

Previously presented evidence of Zn competition for Cd soil sorption sites has been confirmed by detailed studies of two Danish soils. Cadmium distribution between soil and solute decreases for increasing Zn solute concentrations. A Langmuir model accounting for both Cd and Zn sorption onto the same sorption sites was supported by independent experimental data on Cd and Zn distribution. The competition of Zn is governed by the product of the Zn soil sorption stability constant and the actual Zn solute concentration. Cadmium distribution coefficients may be significantly influenced by Zn at Zn solute concentrations above 100 μg Zn dm^?3. This may have implications for interpreting Cd plant uptake and leaching.     

Diffusion of strongly sorbed solutes in soil: a dual-porosity model allowing for slow access to sorption sites and time-dependent sorption reactions

We use homogenization techniques to derive a dual (or double) porosity model of solute diffusion and reaction in soil, allowing for slow access to sorption sites within micro-aggregates and time-dependent sorption reactions. We give a means for determining the conditions in which micro-scale concentration gradients affect macro-scale gradients and fluxes. We present equations for a unit volume of soil represented as a series of uniformly-spaced, porous spherical particles, containing and surrounded by solution through which solutes diffuse. The methods we use can, in principle, be applied to more complex geometries. We compare the model's predictions with those of the equivalent single porosity model for commonly used boundary conditions. We show that failure to allow for slow access to reaction sites can lead to seriously erroneous results. Slow access has the effect of decreasing the sorption of solute into soil from a source or desorption from soil to a sink. As a result of slow access, the diffusion coefficients of strongly-sorbed solutes measured at the macro-scale will be time-dependent and will depend on the method of measurement. We also show that slow access is more often likely to limit macro-scale diffusion than rates of slow chemical reactions per se . In principle, the unimportance of slow reactions except at periods longer than several weeks of diffusion simplifies modelling because, if slow access is correctly allowed for, sorption can be described with equilibrium relations with an understanding of speciation and rapid sorption-desorption reactions.     

Contribution of sorption,DOC transport and microbial interactions to the 14C age of a soil organic carbon profile: Insights from a calibrated process model

Profiles of soil organic carbon (SOC) are often characterized by a steep increase of ¹⁴C age with depth, often leading to subsoil ¹⁴C ages of more than 1000 years. These observations have generally been reproduced in SOC models by introducing a SOC pool that decomposes on the time-scale of millennia. The overemphasis of chemical recalcitrance as the major factor for the persistence of SOC was able to provide a mechanistic justification for these very low decomposition rates. The emerging view on SOC persistence, however, stresses that apart from molecular structure a multitude of mechanisms can lead to the long-term persistence of organic carbon in soils. These mechanisms, however, have not been incorporated into most models. Consequently, we developed the SOC profile model COMISSION which simulates vertically resolved SOC concentrations based on representations of microbial interactions, sorption to minerals, and vertical transport. We calibrated COMISSION using published concentrations of SOC, microbial biomass and mineral-associated OC (MOC), and in addition, ¹⁴C contents of SOC and MOC of a Haplic Podzol profile in North-Eastern Bavaria, Germany. In order to elucidate the contribution of the implemented processes to the ¹⁴C age in different parts of the profile, we performed model-experiments in which we switched off the limitation of SOC decomposition by microbes, sorptive stabilization on soil minerals, and dissolved OC (DOC) transport. By splitting all model pools into directly litter-derived carbon and microbe-derived organic carbon, we investigated the contribution of repeated microbial recycling to ¹⁴C ages throughout the profile. The model-experiments for this site lead to the following implications: Without rejuvenation by DOC transport, SOC in the subsoil would be on average 1700 ¹⁴C years older. Across the profile, SOC from microbial recycling is on average 1400 ¹⁴C years older than litter-derived SOC. Without microbial limitation of depolymerization, SOC in the subsoil would be on average 610 ¹⁴C years younger. Sorptive stabilization is responsible for relatively high ¹⁴C ages in the topsoil. The model-experiments further indicate that the high SOC concentrations in the Bh horizon are caused by the interplay between sorptive stabilization and microbial dynamics. Overall, the model-experiments demonstrate that the high ¹⁴C ages are not solely caused by slow turnover of a single pool, but that the increase of ¹⁴C ages along a soil profile up to ages >1000 years is the result of different mechanisms contributing to the overall persistence of SOC. The dominant reasons for the persistence of SOC are stabilization processes, followed by repeated microbial processing of SOC.     

镉胁迫下钝化剂对菠菜镉吸收累积及土壤微生物群落结构的影响

为了探究镉（Cd）胁迫下不同钝化剂对菠菜Cd吸收转运及根际微生物群落结构的影响,设置不施钝化剂（CK）、单施纳米羟基磷灰石（nHAP）、单施巯基生物炭（TMB）、配施纳米羟基磷灰石+巯基生物炭（HPTB）4个处理,比较各处理的土壤微生物群落结构、土壤化学性质与菠菜生物量及Cd含量。结果表明,各钝化剂处理下菠菜生物量均增加,Cd含量均降低;不同钝化剂对土壤主要优势菌群的组成没有显著影响,但会改变细菌和真菌的相对丰度。主成分分析表明,nHAP对细菌群落结构影响较大,对真菌群落结构影响较小。冗余分析发现,pH是影响细菌群落结构的主要因子,全磷含量是影响真菌群落结构的主要因子。综上所述,单施nHAP能够促进菠菜生长,降低Cd含量,且对微生物群落结构的影响较小。     

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.     

Conceptual model and sensitivity analysis for simulating the extraction kinetics of soil washing

Purpose  

Most previous studies focused on the metal extraction efficiency of chelant-enhanced soil washing under various operational conditions; however, one of the keys to cost-effective field application is to maintain a high throughput rate (i.e., short washing time) while achieving the treatment objectives. Therefore, this study presented a conceptual model for simulating the kinetic extraction of heavy metals and evaluated its sensitivity analysis to the predetermined parameter values in five soils with different initial metal distributions.     

Effect of soil structure on wheat root growth, water uptake and grain yield. A computer simulation model

A model for simulation of wheat root growth under non-optimal conditions has been developed. The following influences on root growth are considered: soil temperature; soil water suction and mechanical resistance dependent on soil density and soil water content; the occurrence of soil cracks. The probability of root tips finding cracks, where unimpeded growth can occur, is given special consideration, including the effect of changes in the crack system with changes in soil water content. Water uptake is calculated, and by use of a transpiration coefficient an estimate of dry-matter production is made. This is partitioned between roots, leaves and stem and later grain. Effects of soil fertility are not yet considered in this model.A sensitivity analysis of the model was made by varying the soil density profile, the occurrence of cracks, sowing date and plant density for several years of weather data. The variability, caused by the fact that only a limited number of root axes was simulated in each run and guided by random numbers, was also investigated.The model can be used to assess the effects of compaction on wheat yield, and also the likely benefits which may be derived from sub-soiling or slit-tillage.The model is written in Digital's VAX FORTRAN language, and a run for one growing season takes less than 10 seconds of CPU-time on a VAX 11/785 computer.     

A model for the impact of soil solution Ca: Al ratio,soil moisture and temperature on tree base cation uptake

A model for tree base cation uptake has been developed, dependent on the soil solution concentration of Al³⁺, divalent base cations such as Ca²⁺, Mg²⁺ and H⁺ ions, modelled with a Mikaelis-Menten type of expression based on the molar BC∶Al ratio, where BC is the sum of the divalent non-toxic base cations Ca²⁺ and Mg²⁺. The expression has the form of counteracting adsorption isoterms for BC and Al to the tree root. The effect of toxic levels of Hg and Pb is incorporated into the model, using root adsorption as the mechanism, and parameterization against experimental data. The expression is modified with an expression accounting for the effect of heavy metal toxicity and soil water content. The dependence of the uptake rate on soil moisture content can be shown to have the form of a Freundlich adsorption isotherm for water. The available data indicate an activation energy of 47 kJ^?1 mol for base cation uptake to trees. Data from the literature was used to estimate the rate coefficients and ion selectivity coefficients for typical coniferous and decideous trees in Sweden and Germany. The model indicates that Ca²⁺ and Mg²⁺ is effective in mitigating Al³⁺ toxicity to tree roots, and that increasing the Ca²⁺+Mg²⁺ soil solution concentration has a promotive effect on base cation uptake. Above a certain limit base cation uptake becomes independent of the solution base cation concentration. This is consistent with field observations, and may be developed to become a tool for assessing the impact of soil chemistry changes on forest growth rate and health status. Field data from the Swedish Forest Survey indicate that uptake depend on the square root of the soil solution base cation availability originating from weathering and deposition input, which is consistent with the BC∶Al expression of the model.     

Magnesium influence on plant uptake of phosphorus in a calcareous soil

A pot experiment was conducted to investigate the role of magnesium (Mg) in plant utilization of ³²phoshorus (P)‐labelled P in a calcareous soil (Typic Hapluquent). Results with two successive harvests of ryegrass shoots indicated that Mg had no obvious influence on plant uptake of the P applied. In a separate incubation study with the same soil, labelled P along with different levels of Mg was introduced to the soil at two time intervals and soil inorganic P was fractionated. The isotope data of P in various fractions indicated that Mg at the test levels had no obvious influence on P transformation either. It is suggested from the experiments that Mg is unlikely to be able to promote plant utilization of fertilizer P in calcareous soils.     

添加物对镉、锌、铅污染土壤上小白菜的生长和养分吸收的影响

A pot experiment was carried out to study the effects of two amendments, lime and calcium magnesium phosphate, on the growth and Cd,Pd,Zn,Cu,Mn,Fe,N,P and K uptake of pakchoi (Brassica chinensis) in a Cd,Pb and Zn polluted acid soil in the southern part of China. The growth of pakchoi was apparently improved by lime and calcium magnesium phosphate application, the uptake of Cd,Pb,Cu and Zn by pakchoi was significantly depressed and the symptom caused by heavy metals pollution was eliminated. Meanwhile, the absorption of N,K and Mn was also inhibited by these amendments. Soil pH was the main factor controlling the uptake of the heavy metals by pakchoi. This suggests that lime and calcium magnesium phosphate could be used as effective amendments for eliminating the toxicity of heavy metals to the vegetable and inhibiting their absorption by the crop.     

Fate and plant uptake of persistent organic pollutants in soil

Many persistent organic pollutants (POPs), notably hexachlorocyclohexanes (HCHs), chlorinated cyclodienes, and dichlorodiphenyltrichloroethanes (DDTs), remain in Japanese farming soils, more than 40 years after their use as insecticides was prohibited. In recent years, residues of chlorinated cyclodienes in cucurbit fruits have become a problem. But, though HCHs and DDTs have been staying in the soil, residues of these chemicals in crops have not been a problem. So we compared the fates of HCHs (α-, β-, γ-HCHs), chlorinated cyclodienes (dieldrin, endrin, heptachlor exo-epoxide), and DDTs (DDE, dichlorodiphenyldichloroethylene; DDD, dichlorodiphenyldichloroethane) in soil and investigated their uptake by several non-cucurbits and cucurbits. As for the fate of POPs in soil, not only the total concentrations but also the concentrations in soil solution as bioavailable POPs were determined. The half-lives of total β-HCH and DDTs in soil were the longest, and α- and γ-HCHs the shortest. On the other hand, the half-lives of bioavailable POPs ranged from 1/3 to 1/20 of those of total POPs. The ratio of the half-lives of bioavailable POPs to those of total POPs decreased in the order of HCHs > chlorinated cyclodienes > DDTs. Because hydrophobic chemicals were adsorbed strongly to the soil, the bioavailable POPs in soil are controlled by their hydrophobicity, indicated by the values of log K _OW (K _OW: n-octanol-water partition coefficient). The shoot concentrations of chlorinated cyclodienes and DDTs were higher in cucurbits than in non-cucurbits. However, among POP insecticides, HCHs did not show clear differences. As for the root concentrations, all tested POPs were higher in cucurbits than in non-cucurbits. Through the determination of POPs in soil solution, we could compare the abilities of plants to take up the chemicals using soil solution bioconcentration factors (BCF_SS). The values of BCF_SS increased with the magnitude of log K _OW, in the order of HCHs < chlorinated cyclodienes < DDTs. In addition, BCF_SS did not show marked differences among isomers or chemicals with similar structure. Therefore, plant uptake ability was influenced mainly by log K _OW. After being applied to agricultural land, α- and γ-HCHs seemed to disappear quickly, β-HCH persisted longer but the uptake in roots was low because of the low log K _OW, and DDTs also persisted longer but the bioavailability decreased rapidly in the soil because of their high log K _OW. Chlorinated cyclodienes have remained in the soil and have remained available, because they are less likely than HCHs (except β-HCH) to disappear and less likely than DDTs to become adsorbed to the soil. In addition, their higher log K _OW than that of HCHs makes them more easily taken up by roots. However, shoot concentrations were high only in cucurbits, for which they remain a problem in Japan.