Toluene sorption behavior on soil organic matter and its composition using three typical soils in China

The effect of soil organic matter (SOM) content and composition on sorption behavior of toluene for fluvo-aquic, red and black soils in China was investigated in batch experiments. Tested SOM was fractionated into two primary sorptive domains (‘soft’ and ‘hard’) to explain the dependence of sorption behavior on SOM composition. All the tested soils exhibited similar sorption kinetics and nonlinear sorption isotherms. Soils with high SOM content possessed a high sorptive capacity. Clay minerals also contributed to the sorptive capacity, especially for fluvo-aquic and red soils with low SOM content. In comparison, after removing most ‘soft’ SOM fraction from soils through hydrogen peroxide treatment, the residual ‘hard’ SOM fraction of three soil samples exhibited a slower sorption rate and a less sorption capacity compared to the untreated soil samples. The nonlinear degree of sorption was positively correlated with the content of ‘hard’ SOM for all soil samples. This is explained by the combined effect of SOM content and the composition on toluene sorption rates, sorption capacity and nonlinear degree of sorption of three typical soils in China.     

Effects of organic matter heterogeneity on sorption and desorption of organic contaminants by soils and sediments

This review highlights the major progress over the last decade on characterization of geochemically heterogeneous soil/sediment organic matter (SOM) and the impacts of SOM heterogeneity on sorption and desorption of hydrophobic organic contaminants (HOCs) under equilibrium and rate limiting conditions. Sorption and desorption by soils and sediments are fundamental processes controlling fate and transport of less polar and nonpolar organic pollutants in surface aquatic and groundwater systems. Recent studies have shown that soils and sediments exhibit an array of HOC sorption phenomena that are inconsistent with an early partition model based on an assumption of homogeneous gel-like SOM. Increasing data have revealed that isotherm nonlinearity, varied sorption capacity, sorption–desorption hysteresis, and slow rates of sorption and desorption are characteristics for HOC sorption by soils and sediments. These phenomena have been shown to result from different types of condensed SOM that exhibit capacity limiting sorption processes. Recent findings of glass transition phenomena and the nonlinear HOC sorption by humic acids provide a scientific foundation for drawing an analogy between humic acids and synthetic organic polymers that supports a dual mode model for sorption by soils and sediments. Humic acid is glassy or rigid at temperatures lower than its glass transition temperature and exhibits relatively nonlinear sorption isotherms for HOCs. Fractionation and quantification of SOM indicate that soils and sediments contain significant amounts of black carbon and kerogen of different origins. These particulate organic materials have rigid 3-dimensional structures and are often less polar compared to humic substances. Limited studies show that black carbon and kerogen exhibit nonlinear sorption for HOCs and may dominate the overall nonlinear sorption by soils and sediments.     

Effect of organic matter and selected heavy metals on sorption of acenaphthene,fluorene and fluoranthene onto various clays and clay minerals

The effects of organic matter (80% humic and 15% fulvic acid) and coexistence of heavy metals (Ni, Pb and Zn) on sorption of three polycyclic aromatic hydrocarbons (PAHs)—acenaphthene, fluorene and fluoranthene—were examined for kaolinite, 60% kaolinite?+?40% sand, and 43% kaolinite?+?42% sand?+?15% bentonite. In total 108 batch sorption tests of PAHs were conducted for three types of clay mineral mixtures in six possible combinations of soil organic matter and heavy metal contents from no heavy metals and organic matter added to maximum organic matter added with spiked heavy metals. Results showed that the existence of metals increased the sorption of PAHs onto kaolinite from 4.7% for acenaphthene to 17.9% for fluoranthene. Organic matter in a kaolinite-sand-bentonite matrix could increase PAH sorption by up to 140% for fluoranthene. In all cases, increases were greater for fluoranthene, a larger PAH molecule. Heavy metals coexisting with organic matter led to enhanced sorption of PAHs compared to clay minerals without organic matter. Synergistic effects of organic matter and heavy metals on PAH sorption increments in the mixtures studied were such that the overall sorption could be 10–41% higher than that based on summation of the separate effects of metals and organics.     

红壤中矿物表面对腐殖质吸附萘的影响

矿物表面可改变土壤腐殖质对疏水性有机污染物的结合能力。采用红壤和高岭石分别与胡敏酸结合制备得到的两种复合体对萘的吸附等温线非线性显著,其n=0.76或0.74,并且有机碳归一化吸附分配系数的实验值Koacds是采用Kow计算得出的理论值Koc的5倍以上,表明红壤、高岭石均对腐殖质吸附萘有强化作用,且红壤较之高岭石对腐殖质吸附萘的影响稍强些。主要原因是,红壤中除了高岭石外,还有与腐殖质结合力很强的铁氧化物,而且很可能是吸附态腐殖质组成结构形态发生了有利于对萘吸附的改变。     

Mechanistic roles of soil humus and minerals in the sorption of nonionic organic compounds from aqueous and organic solutions

Mechanistic roles of soil humus and soil minerals and their contributions to soil sorption of nonionic organic compounds from aqueous and organic solutions are illustrated. Parathion and lindane are used as model solutes on two soils that differ greatly in their humic and mineral contents. In aqueous systems, observed sorptive characteristics suggest that solute partitioning into the soil-humic phase is the primary mechanism of soil uptake. By contrast, data obtained from organic solutions on dehydrated soil partitioning into humic phase and adsorption by soil minerals is influenced by the soil-moisture content and by the solvent medium from which the solute is sorbed.     

苯和甲苯在土壤中的吸附行为研究

选取某采油厂不同有机碳含量的表层土壤作为吸附剂,采用批实验方法对原油中代表性组分苯和甲苯的单组分吸附和双组分竞争吸附行为进行了研究。研究表明,单组分溶液中,苯和甲苯在土壤中的吸附符合线性规律,吸附能力与土壤有机碳含量成正比;双组分溶液中,苯和甲苯共存时存在竞争吸附,土壤对它们的吸附小于单组分时的情况。竞争吸附的结果说明,除分配吸附以外,介质表面点位对苯和甲苯的吸附也起着重要的作用。     

Sorption of inorganic mercury and monomethyl mercury in an iron–humus podzol soil of southern Norway studied by batch experiments

Considerable fractions of the Hg content of lake and river systems in Scandinavia are discharged from the soil of the catchments. An important soil type in Scandinavia is the iron–humus podzol. The sorption characteristics of this soil type for inorganic Hg(II) and monomethyl mercury were investigated by batch experiments. The solubility of Hg²⁺ and CH₃Hg⁺ in the soil horizons containing organic matter increases with increasing pH of the soil solution by favoring the formation of solute organic matter–mercury complexes. While the solubility of Hg²⁺ is strongly dependent on complexation to dissolved organic matter, the solubility of CH₃Hg⁺ is more dependent on ion exchange. The concentration of solute inorganic Hg(II) increased with increasing temperature probably because of an increase in the concentration of dissolved organic carbon. There was no effect of temperature on the concentration of solute CH₃Hg⁺. At pH values where inorganic mercury–hydroxo complexes are formed, inorganic Hg(II) is efficiently sorbed to the metal oxides of the mineral soil. The soil–water distributions of inorganic Hg(II) in the different soil horizons were described by Freundlich isotherms or linear isotherms for common and contaminated mercury contents in the soils.     

Distribution and sorption of potentially toxic metals in four forest soils from Hungary

Metals of natural and anthropogenic origin behave differently in soils mostly due to their different mobility. In this study, sequential extractions and batch sorption experiments were performed to relate the fractionation of native Ni, Cu, Zn and Pb to the sorption properties of added metals in four soils with contrasting physiochemical characteristics. A significant effect due to sample composition on both the mobility and sorption characteristics of these metals was found. The efficiency of soil components in metal immobilization was in the order of carbonate > organic matter > swelling clay minerals. The partitioning of native metals together with the information gained through the sorption isotherms allows a deeper insight on the fate and behavior of metals in soils with various compositions.     

A detailed pyrolysis-GC/MS analysis of a black carbon-rich acidic colluvial soil (Atlantic ranker) from NW Spain

Despite the potentially large contribution of black carbon (BC) to the recalcitrant soil organic matter pool, the molecular-level composition of aged BC has hardly been investigated. Pyrolysis-GC/MS, which provides structural information on complex mixtures of organic matter, was applied to the NaOH-extractable organic matter of an acidic colluvial soil (Atlantic ranker) sampled with high resolution (5 cm) that harbours a fire record of at least 8.5 ka. Additionally, 5 charcoal samples from selected soil layers were characterised using pyrolysis-GC/MS for comparison. Pyrolysis-GC/MS allowed distinguishing between BC and non-charred organic matter. It is argued that a large proportion of the polycyclic aromatic hydrocarbons (PAHs), benzenes and benzonitrile in the pyrolysates of the extractable organic matter, together accounting for 21–54% of total identified peak area, derived from BC. In charcoal samples, these compounds accounted for 60–98% of the pyrolysis products. The large quantity of BC in almost all samples suggested a key role of fire in Holocene soil evolution. The high C content of the soil (up to 136 g C kg⁻¹ soil) may be attributed to the presence of recalcitrant organic C as BC, in addition to the sorptive preservation processes traditionally held responsible for long-term C storage in acid soils. Interactions between reactive Al hydroxides and BC could explain the longevity of BC in the soil. This work is the first thorough pyrolysis-GC/MS based study on ancient fire-affected organic matter.     

Citrate sorption and biodegradation in acid soils with implications for aluminum rhizotoxicity

Citrate and other organic acids play an important role in the rhizosphere and pedogenic processes. Although secreting citrate from roots in response to Al and heavy metal stress has been recognized as a central mechanism for plants to avoid toxicity, the efficiency of root citrate on metal detoxification is still contradictory in acid soil with abundant oxide minerals that serve as a potential sorption site for citrate. The objective of this study was to investigate sorption and biodegradation of citrate in subtropical acid soils with different mineralogical properties. A batch experiment was conducted to assess the possible fates (adsorption and biodegradation) of citrate in the three acid soils (Cecil, Creedmoor and Norfolk) under microbial-active and inactive conditions. Citrate adsorption isotherms for all soils were adequately described by the Freundlich equation with the R² value being over 0.90. The Cecil soil had the highest affinity for citrate adsorption among the soils with 99% adsorption observed throughout the citrate concentration range, which was due primarily to the abundant Al and Fe oxides. Citrate sorption to the mineral phase significantly reduced its biodegradation by 56%, 65% and 99% for the Creedmoor, Norfolk and Cecil soils, respectively. The results suggest the efficiency of rhizosphere processes for Al detoxification by root-secreted citrate would be significantly reduced in acid soil with abundant Al and Fe oxides.     

Variation in lipid relative abundance and composition among different particle size fractions of a forest soil

Most studies of soil organic matter are on humic substances although a substantial contribution of lipids is generally noted for soils. Moreover, soil lipids were shown to have a relatively high resistance to biodegradation. Thus, they could provide information on organic matter sources and diagenetic processes. Soil organic matter is highly heterogeneous and different dynamic pools are in evidenced. However the links between these pools and molecular structure have not yet been established. Soil lipids were investigated in three particle-size fractions of a forest soil. Lipids were shown to be preferentially located in the finest fraction. GC-MS analysis of free lipids has revealed different main sources depending on the particle-size fraction and differential degradation. Furthermore, the results obtained for the free lipids on the one hand, and the saponified lipids on the other hand, have indicated that different preservation mechanisms for lipids occur in this soil.     

Sorptive stabilization of organic matter in soils by hydrous iron oxides

Strong correlations between iron oxides (FeOx) and organic matter (OM) in soils have implied the importance of the former in stabilizing the latter. One mechanism thought to be important in this stabilization is sorption. We tested this possibility by reductively dissolving FeOx in a wide variety of soils and measuring the organic carbon (OC) that was solubilized. The OC dissolved from non-FeOx phases via anion exchange was corrected for by parallel control extractions. The resultant pool, reductively soluble OC, made up a minor amount of total soil OC in all but one of these soils, indicating that simple sorption reactions do not stabilize the bulk of soil OC in most mineral soils. OC:Fe ratios in the extracts from 2/3 of these soils were less than 0.22 (wt/wt), consistent with a sorbed state for this OC and showing that OC sorption by FeOx in these soils is limited by the amount of FeOx. The remaining soils had low pH and high OM concentrations; their higher OC:Fe ratios indicate inclusion of precipitated organo-Fe complexes in the extracts, which are likely only partially extracted by our method. The high volumetric ratios of OM to FeOx found in correlations between them from the literature are inconsistent with a dominant sorption control and point instead to stabilization to other mechanisms such as organo-Fe complexes or ternary associations among FeOx, OM and other minerals.     

煤中干酪根的成熟度与菲的吸附行为间的关系

将云南先锋褐煤采用热模拟的实验方法制得一组成熟度不同的煤,并将煤中的干酪根用于对菲的吸附研究.结果表明:随着干酪根成熟度的增加,有机质结构变得紧密、刚硬,还原性和芳香性增强.不同成熟度干酪根的内部结构和性质与菲的吸附行为间存在一定的关系.随着干酪根内部结构的刚性和芳香性的增强,吸附等温线的非线性逐渐增强.对于成熟度相对较低的干酪根,随着成熟度的增加,吸附容量逐渐增大,而对于成熟度相对较高的干酪根,随着成熟度的增加,吸附容量却减小.     

A surface complexation and ion exchange model of Pb and Cd competitive sorption on natural soils

The bioavailability and fate of heavy metals in the environment are often controlled by sorption reactions on the reactive surfaces of soil minerals. We have developed a non-electrostatic equilibrium model (NEM) with both surface complexation and ion exchange reactions to describe the sorption of Pb and Cd in single- and binary-metal systems over a range of pH and metal concentration. Mineralogical and exchange properties of three different acidic soils were used to constrain surface reactions in the model and to estimate surface densities for sorption sites, rather than treating them as adjustable parameters. Soil heterogeneity was modeled with >FeOH and >SOH functional groups, representing Fe- and Al-oxyhydroxide minerals and phyllosilicate clay mineral edge sites, and two ion exchange sites (X⁻ and Y⁻), representing clay mineral exchange. An optimization process was carried out using the entire experimental sorption data set to determine the binding constants for Pb and Cd surface complexation and ion exchange reactions.Modeling results showed that the adsorption of Pb and Cd was distributed between ion exchange sites at low pH values and specific adsorption sites at higher pH values, mainly associated with >FeOH sites. Modeling results confirmed the greater tendency of Cd to be retained on exchange sites compared to Pb, which had a higher affinity than Cd for specific adsorption on >FeOH sites. Lead retention on >FeOH occurred at lower pH than for Cd, suggesting that Pb sorbs to surface hydroxyl groups at pH values at which Cd interacts only with exchange sites. The results from the binary system (both Pb and Cd present) showed that Cd retained in >FeOH sites decreased significantly in the presence of Pb, while the occupancy of Pb in these sites did not change in the presence of Cd. As a consequence of this competition, Cd was shifted to ion exchange sites, where it competes with Pb and possibly Ca (from the background electrolyte). Sorption on >SOH functional groups increased with increasing pH but was small compared to >FeOH sites, with little difference between single- and binary-metal systems. Model reactions and conditional sorption constants for Pb and Cd sorption were tested on a fourth soil that was not used for model optimization. The same reactions and constants were used successfully without adjustment by estimating surface site concentrations from soil mineralogy. The model formulation developed in this study is applicable to acidic mineral soils with low organic matter content. Extension of the model to soils of different composition may require selection of surface reactions that account for differences in clay and oxide mineral composition and organic matter content.     

有机组分土-水分配系数的确定(英文)

有机组分的土水分配系数(Kd)是描述有机组分在地下系统中吸附特征的重要参数。同时,它也是物质运移模拟和环境评价中的主要参数之一。影响Kd的因素可概括为三个方面:土壤性质、有机组分本身特征及水相的物理化学性质。一般而言,对于非极性和弱极性有机组分,土壤中的有机质含量(foc )是影响Kd的最主要因素。但是,对于极性有机组分(POCs), 特别是在土壤有机质含量较低的情况下,土壤中矿物的种类和含量、水化学组分特征(pH、离子力等)经常在吸附过程中起重要作用。实验室内测定Kd的方法包括批实验和柱实验方法。批实验法适用于研究Kd较高情况下的吸附。在Kd较低的情况下,如低有机质土壤对极性有机污染物的吸附,土柱色谱法(SCC)是更适宜的选择。另外,可用土柱色谱法快速了解各种因素对吸附过程的影响,并获取详细的吸附和解吸信息。应用土柱色谱法时应当注意非平衡吸附和可能的柱堵塞问题。很多文献中提到结合柱实验和已有的吸附数据来预测土壤有机碳标准化的分配系数Koc(=Kd/foc)。但是,如果没有考虑吸附中特定的作用过程(如矿物吸附),对极性有机组分Koc的预测将会产生很大的误差。在环境评价中,将从一种土壤测定的Koc 应用到不同性质的土壤中,可能会导致错误的认识。在进行室内实验时,应把标准土(如Eurosoi     

The development of a multi-surface soil speciation model for Cd (II) and Pb (II): Comparison of two approaches for metal adsorption to clay fractions

The mobility of toxic metals in soils or sediments is of great concern to scientists and environmentalists since it directly affects the bioavailability of metals and their movement to surface and ground waters. In this study, a multi-surface soil speciation model for Cd (II) and Pb (II) was developed to predict the partition of metals on various soil solid components (e.g. soil organic matter (SOM), oxide mineral, and clay mineral). In previous study, the sorption of metal cations on SOM and oxide minerals has been evaluated by thermodynamically based surface complexation model. However, metal binding to soil clay fractions was normally treated in a simplistic manner: only cation exchange reactions were considered and exchange coefficient was assumed unity. In this study, the binding of metals onto clays was described by a two-site surface sorption model (a basal surface site and an edge site). The model was checked by predicting the adsorption behavior of Cd (II) and Pb (II) onto three selected Chinese soils as a function of pH and ionic strengths. Results showed that the proposed model more accurately predicted the metal adsorption on soils under studied condition, especially in low ionic strength condition, suggesting that adsorption of metals to soil clay fractions need to be considered more carefully when modeling the partition of trace elements in soils. The developed soil speciation model will be useful when evaluating the movement and bioavailability of toxic metals in soil environment.     

水稻土中重金属元素Cd、Pb的竞争吸附 ——以长株潭地区水稻土为例

对中国南方的3个水稻土样品进行了Cd、Pb单一离子和混合离子吸附特点的研究。结果表明,3个水稻土样品中Cd、Pb的吸附特点都相似,Langmuir等温方程可很好地描述Cd、Pb的吸附等温线。3个土壤样品中,有较高pH值和较低有机物、CEC浓度、粘土含量、高岭石含量的2个土壤样品对Cd、Pb有较大的吸附量,且其等温吸附拟合的最大吸附量(B)也较大。在两组分混合溶液中,尽管共存离子的存在影响了土壤对单一离子的吸附,同时土壤对Cd的吸附在一定程度上受影响的程度大,但3个土壤样品都表现出对Pb有强的吸附能力。在3个土壤样品中,Langmuir等温方程中Pb的健合能常数(K)都大于Cd的健合能常数(K),混合溶液中的K值高于单一溶液的K值,表明2种金属离子对吸附位点的竞争提高了特定吸附位点的保持力,使金属离子在土壤中特定位点的吸附更加坚固。     

Effects of Soil Composition on Zn Speciation in Drainage Waters from Agricultural Soils

The influence of Zn speciation on Zn transport by drainage from different soils to surface water is examined in a stream catchment in an agricultural area. Drainage waters were collected from two types of soils, a mineral soil (MS) and a soil rich in organic matter (OS) by means of artificial drainage pipes. The speciation of dissolved Zn in the stream and the drainage waters was determined using ligand-exchange and voltammetry. About 50–95% of dissolved Zn is bound in strong complexes, and the free Zn²⁺ ion concentration is in the range of 1–16% of dissolved Zn. A substantial part of Zn is present in weaker organic or inorganic complexes. The simulated Zn speciation using the WHAM VI model is compared to the determined speciation. Free Zn²⁺ concentrations predicted by the WHAM VI model are generally higher than the analytically determined free Zn²⁺, but are mostly within the same order of magnitude. Effects of different soil organic matter content on Zn speciation and transport are discussed. Zn speciation in the drainage at the OS site is influenced by the distribution of organic matter between the solid and solution phase. The abundant organic Zn complexes in solution contribute to facilitate Zn transport from soil into surface waters, through the drainage at the OS site. Drainage from the OS site contributes about twice as much Zn input to the receiving water as the MS soil, as related to specific area. The mineral soil contains much lower organic matter, and a part of Zn bound with inorganic phases can hardly be released by dissolved organic ligands, leading to much higher Zn retention at the MS site.     

Effects of geosorbent and solution properties on sorption and desorption of PAHs

Characteristics of phenanthrene and pyrene’s sorption and desorption on two local soils in solutions of simulated groundwater, simulated lung fluid, and simulated saliva were studied with batch equilibrium experiments to understand the fate of PAHs in the karst region of southwestern China and to assess the environmental exposure and the health risk of PAHs. The results showed that the sorption and desorption isotherms of phenanthrene and pyrene on two target soils in the three solution systems could be adequately described by the Freundlich model, while the fitted isotherm parameters for the simulated groundwater solution distinguished notably from those for the simulated body fluid solutions. For the sorption experiments, in the simulated groundwater, the n values were 0.722 and 0.672 for phenanthrene and were 0.724 and 0.663 for pyrene, respectively, on the yellow soil and the limestone soil; The log K_F values were 3.118 and 3.323 for phenanthrene and were 3.648 and 3.846 for pyrene, respectively, on the yellow soil and the limestone soil. In the simulated body fluids, the n values for phenanthrene and pyrene ranged from 0.622 to 0.836 and from 0.590 to 0.865, respectively, and the log K_F values of phenanthrene and pyrene ranged from 2.845 to 3.327 and from 3.344 to 3.779, respectively. For the desorption experiments, in the simulated groundwater, the n values were 0.662 and 0.744 for phenanthrene and were 0.702 and 0.647 for pyrene, respectively, on the yellow soil and the limestone soil. The log K_F values were 3.666 and 3.686 for phenanthrene and were 4.128 and 4.225 for pyrene, respectively, on the yellow soil and the limestone soil. In the simulated body fluids, the n values for phenanthrene and pyrene ranged from 0.612 to 0.668 and from 0.631 to 0.819, respectively, and the log K_F values of phenanthrene and pyrene ranged from 3.134 to 3.407 and from 3.533 to 3.839, respectively. The limestone soil had relatively higher log K_F values but lower K_OC values compared to those of the yellow soil, indicated that the nature of sorbent soils played the dominant role in sorption and desorption behaviors of PAHs. The experimental results showed a remarkable differences in sorption and desorption behaviors of PAHs in simulated body fluids and groundwater. The nonlinearities of measured isotherms and the measured sorption capacities of soils in simulated body fluids were significantly lower than corresponding those in the simulated groundwater, and HI values for simulated body fluids systems were significantly smaller than corresponding those for the simulated groundwater systems. The results underscore cautions in assessing environmental exposure and health risks of PAHs based on their sorption–desorption data in simulated groundwater as this is traditionally done.

     

水稻土中重金属元素Cd、Pb的竞争吸附——以长株潭地区水稻土为例

对中国南方的3个水稻土样品进行了Cd、Pb单一离子和混合离子吸附特点的研究。结果表明,3个水稻土样品中Cd、Pb的吸附特点都相似,Langmuir等温方程可很好地描述Cd、Pb的吸附等温线。3个土壤样品中,有较高pH值和较低有机物、CEC浓度、粘土含量、高岭石含量的2个土壤样品对Cd、Pb有较大的吸附量,且其等温吸附拟合的最大吸附量（B）也较大。在两组分混合溶液中,尽管共存离子的存在影响了土壤对单一离子的吸附,同时土壤对Cd的吸附在一定程度上受影响的程度大,但3个土壤样品都表现出对Pb有强的吸附能力。在3个土壤样品中,Langmuir等温方程中Pb的健合能常数（K）都大于Cd的健合能常数（K）,混合溶液中的K值高于单一溶液的K值,表明2种金属离子对吸附位点的竞争提高了特定吸附位点的保持力,使金属离子在土壤中特定位点的吸附更加坚固。