有机磷与土壤矿物相互作用及其环境效应研究进展

土壤有机磷是土壤环境中重要的磷组分,其在环境中的界面反应影响着磷素的迁移、转化、生物有效性以及环境行为。本文主要总结了土壤中典型有机磷在矿物表面的吸附-解吸、溶解-沉淀等反应特性和微观机制,以及有机磷-矿物相互作用对有机磷形态、金属离子界面反应行为,以及矿物胶体化学稳定性与溶解转化的影响等环境效应。土壤有机磷可含多个磷酸基团,相对分子质量大,电荷密度高,通过界面反应与环境矿物发生强烈的相互作用,并影响矿物的电荷性质、共存金属离子的吸附特性、以及胶体化学稳定性。有机磷界面反应特性和机制受矿物类型和结晶度、有机磷相对分子质量、pH、温度和共存离子等因素的影响。有机磷在矿物表面的吸附密度一般随着体系pH、矿物结晶度和有机磷相对分子质量的升高而降低。有机磷一般可在矿物表面形成内圈络合物,某些情况下还存在氢键作用,甚至转化形成表面沉淀。有机磷和金属离子在矿物表面的吸附一般存在协同效应(尤其是在低pH条件下),即金属离子促进了有机磷的吸附,有机磷也促进金属离子的固定;吸附机制因反应体系而异,主要包括形成三元表面络合物和表面沉淀等,多数时候存在多种机制的共同作用。最后讨论了环境中有机磷与矿物相互作用的主要研究热点和方向。     

磷酸根在矿物表面的吸附-解吸特性研究进展

综述了磷酸根在一些常见土壤矿物表面吸附–解吸特性的研究进展。磷酸根在矿物表面的吸附特性受环境pH、离子强度、温度、反应时间、矿物类型等多种因素的共同影响。一般说来,矿物表面的磷吸附量随pH降低而增加,受离子强度的影响较小。磷酸根在矿物表面的吸附动力学过程可分为快速吸附过程和慢速吸附过程,且在弱结晶矿物中存在微孔扩散过程。磷酸根在矿物表面的解吸过程通常存在两个阶段(初始快速解吸和随后的缓慢解吸),在解吸反应后期甚至还会发生再吸附。此外,磷酸根的吸附特性也受共存阴离子配体或金属阳离子的影响。其中,共存阴离子通过位点竞争、静电作用和空间位阻效应等机制影响磷酸根的吸附。天然有机质(包括胡敏酸和富里酸)降低了磷酸根在矿物表面的吸附,特别是在低p H条件下。通常,富里酸比胡敏酸更能有效降低磷酸根在矿物表面的吸附。金属阳离子可通过表面静电效应、形成三元络合物以及形成表面沉淀等机制促进磷酸根和金属在矿物表面的共吸附。最后,展望了与磷酸根在矿物表面吸附特性有关的研究热点和方向。     

蒙脱石-氧化铁二元复合胶体吸附钨的研究

本研究选取代表性层状硅酸盐蒙脱石，两种代表性氧化铁(水铁矿、针铁矿)，合成蒙脱石-水铁矿、蒙脱石-针铁矿二元复合体，通过宏观吸附以及光谱学技术探究钨(WO₄^2-)在蒙脱石-氧化铁复合体上的吸附行为和潜在机制。结果表明：氧化铁紧密覆盖在蒙脱石表面，使表面颗粒更加细小；钨的吸附量随pH升高而降低，3种吸附剂对钨吸附量大小顺序为：蒙脱石-水铁矿>蒙脱石-针铁矿>蒙脱石；原位红外光谱实验表明，钨在蒙脱石表面主要以外圈络合物形式存在，而在蒙脱石-氧化铁复合体上形成内圈络合物(Fe-O-W)，且在低pH时，形成聚合态钨；X-射线光电子能谱进一步表明，针铁矿和水铁矿表面铁羟基参与了钨的络合反应。本研究证实，氧化铁覆盖不仅增大蒙脱石对钨的吸附量，而且使钨由外圈络合物形态转变为内圈络合态，进一步生成聚合态钨。研究结果对预测钨在土壤中的迁移转化、生物有效性和归宿有重要指导意义。     

铁氧化物-胡敏酸复合物对磷的吸附吸附

本试验通过设置不同磷酸根浓度、 pH和不同电解质及电解质强度梯度,研究磷酸根在针铁矿-胡敏酸（HA）复合物和赤铁矿-胡敏酸（HA）复合物表面的吸附特性。X射线衍射（XRD）、 扫描电镜（SEM）和红外光谱（FTIR）图谱显示: 铁氧化物包覆胡敏酸后其内部结构特性保持不变; 氧化铁与胡敏酸通过氢键形成粒径大、 表面光滑的铁氧化物-HA复合微粒,且复合物比表面减小; 形成的氧化铁-胡敏酸复合物对磷的吸附能力增强,且针铁矿复合物的吸附能力大于赤铁矿复合物,均为多层吸附过程; pH增高抑制铁氧化物复合物对磷的吸附,同时电解质浓度增加促进复合体对磷的吸附,且反应后体系pH随之降低。     

pH对土壤吸持磷酸根的影响及其原因

本文选择了浙江、江苏15个性质变化范围较大的土壤样品,研究在两种支持电解质、不同pH条件下对磷酸根的吸持反应。结果表明,加碱提高强酸性土壤的pH值,导致交换性铝的水解和羟基铝聚合物的生成,增加对磷的吸持。磷酸根同酸性土壤的反应,可促进交换性铝的水解,释放出H⁺,降低体系的pH。在CaCl₂介质中,当pH>6时,可能有磷酸钙类盐形成,使溶液中磷浓度显著降低。有机质对土壤吸持磷有重要影响。在低pH下有机质通过与Al³⁺形成络合物,阻碍溶液中A1³⁺的水解,并与磷酸根竞争羟基铝化合物表面的反应点位,从而降低酸性土壤对磷酸根的吸附量。     

电解质种类和浓度影响磷酸根解吸的机理研究

本文研究了吸附性阳离子、电解质浓度和组成影响几种矿物和土壤吸附态磷的解吸的机理。结果表明,吸附性阳离子影响磷酸根解吸与离子桥有关。桥接静电场愈强,被束缚磷的释放就愈困难。电解质阳离子对磷酸根解吸的影响则取决于其对表面负电荷的屏蔽效应。阳离子电价高,屏蔽作用大,磷解吸就少。电解质浓度影响吸附态磷的解吸主要与表面电位的变化有关。当pH>PZC值时,提高电解质浓度降低表面负电位,从而减少磷的吸附;当pH<PZC时,提高电解质浓度则降低表面正电位,促进磷的解吸。磷酸根解吸盐效应零点(P_PZSE)值一般都介于土壤或矿物样品吸附磷酸根前后测得的两个PZC值之间。不同浓度电解质溶液中磷解吸量之差与吸附层电位变化量(△ψ_x)呈正相关。     

有机阴离子对磷酸根吸附的影响

在中性条件下,低浓度的柠檬酸、草酸、酒石酸和胡敏酸阴离子都能显著降低针铁矿、非晶氧化铝、高岭石和红壤对磷酸根的吸附,尤其在低磷吸附饱和度下效果更好。有机阴离子抑制磷酸根吸附的能力因有机酸的种类和性质、以及固相的表面特性而异。有机阴离子存在下吸附的磷酸根具有较高的同位素³²P交换活性和解吸率。测定了吸附平衡溶液中铁和铝的浓度。结果表明,在实验条件下(pH 7.0),即使较高浓度的有机酸根(10^-2mol)也只能溶解极少量的铁和铝。有机阴离子络溶作用不足以说明固相吸附磷能力的显著下降。可见,有机阴离子降低磷酸根吸附的机制主要是竞争专性吸附。有机阴离子占据了一部分高亲和力的吸附位,从而降低了土壤固相吸附磷的量,增加了吸附态磷的活性。     

畜禽粪便生物炭内源重金属在酸性土壤中的迁移转化

为探究生物炭内源重金属在酸性土壤中的迁移转化规律,科学指导畜禽粪便生物炭农田应用,该研究以猪粪生物炭为研究对象,开展土壤培养试验,利用扫描电镜、物理吸附、X射线衍射物相分析、X射线光电子能谱和电感耦合等离子体质谱等方法表征不同培养时间生物炭表面形貌、孔隙结构、元素分布的变化规律,以及土壤孔隙溶液中重金属、磷酸盐等组分的变化规律。结果显示生物炭内源重金属Cu、Zn主要存在形态为氧化提取态,Cu、Zn氧化提取态比例分别为79.37%和53.43%,生物炭矿物质元素主要以氧化物形式存在于生物炭颗粒表面,施入酸性土壤后,生物炭比表面积及孔容增加,颗粒表面Cu、P、K等元素含量降低,土壤孔隙溶液中pH值、EC、Cu与PO43-含量显著升高,PO43-的浓度范围为2.26～298.00 mg/L,Cu的浓度范围为1.81～2.86 μg/L,生物炭颗粒粒径越小,PO43-和Cu溶出率越高,生物炭施入土壤30 d时,土壤孔隙溶液中PO43-和Cu的浓度最高。研究表明酸性土壤可促进以碳酸盐、磷酸盐氧化物形式存在的Cu以及被碳酸根与磷酸根沉淀的Cu不断释放进入土壤,但生物炭内源Zn在酸性土壤环境不易释放,且生物炭可吸附土壤中的Zn,降低Zn的生物有效性。     

As(Ⅲ)在可变电荷土壤中的吸附与氧化的初步研究

用一次平衡法研究了两种可变电荷土壤与As(Ⅲ)之间的吸附和氧化还原反应。结果表明,当As(Ⅲ)溶液平衡浓度由0·25上升到1·0mmolL-1,砖红壤对砷的吸附量由15·0增加至25·9mmolkg-1,红壤由7·6增至13·0mmolkg-1,砖红壤对砷的吸附量约为红壤的2倍,这是因为前者铁、铝氧化物的含量高于后者。在pH3~7范围内,土壤对As(Ⅲ)的吸附量随pH的增加而增加。砖红壤中的氧化锰能将As(Ⅲ)氧化为As(V),砷的氧化量在pH3~7范围内随体系pH的增加而减小。砷在红壤中的氧化反应不显著。用1·0molL-1的KNO3对吸附性砷进行解吸的结果表明,砷的解吸率在35%以下,说明大部分砷通过形成内圈型表面络合物为土壤所吸附。在pH2~7范围内,砷的解吸率随吸附体系pH的升高而增加,说明较高pH下外圈型表面络合物的比例增加。     

土壤中砷吸附机理及其影响因素研究进展

土壤中砷(As)的生物可利用性、迁移、转化及归宿在很大程度上依赖于其在土壤中的吸附反应.本文首先概述了土壤中As污染物的主要形态、价态及其与吸附的关系,较为系统地介绍了土壤中As吸附的主要影响因素和土壤中As吸附机理等方面的最新研究进展,并重点对X-射线吸收精细结构光谱(XAFS)、红外光谱(IR)等现代分析技术和方法在As吸附研究中的应用和进展进行了论述.由于土壤组分与结构的复杂性,As在环境介质中的吸附机理研究目前仍集中在单纯矿物上的吸附行为,为As在土壤中的吸附研究提供了理论基础.X-射线吸收精细结构光谱及红外光谱研究结果证明As在土壤中的吸附主要与含Fe、Al等矿物结合,形成以双齿双核结构为主的配位结构;其吸附机理与土壤矿物及As污染物的价态、吸附浓度等有关,主要包括表面络合反应和表面沉淀作用:但是土壤中As吸附机理研究还需要进一步深入研究.文章最后分析了有关土壤中As吸附研究的发展趋势和重要动向.     

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.     

Interactions of organic phosphorus with soil minerals and the associated environmental impacts: A review

As an important part of the soil phosphorus(P) pool, organic P(OP) is widely found in terrestrial and aquatic environments(e.g., soils and sediments).The interfacial behavior of OP on natural minerals affects the transport, transformation, and bioavailability of P in the environment. This paper reviews the processes involving adsorption-desorption, dissolution-precipitation, and enzymatic/mineral-mediated hydrolysis of OP at the mineral-water interface, and their subsequent effects on OP speciat...     

矿物基蚯蚓粪表面特征及其对土壤Cd钝化能力的研究

针对农田土壤镉（Cd）活性高的问题,以寻求具有良好重金属钝化特性的原位修复材料为目标,该研究以铁粉、磷矿粉和牛粪混合蚯蚓堆肥所制备的矿物基蚯蚓粪为研究对象,利用系列结构表征手段对其进行基本性质表征,并进一步分析矿物基蚯蚓粪施加下土壤对Cd吸附、有效性和赋存形态的影响,最终筛选出具有良好Cd钝化效果的矿物基蚯蚓粪。结果表明,铁粉及磷矿粉的添加使矿物基蚯蚓粪中的pH值、C/N、有机质含量有所降低,但总养分含量显著增加（P<0.05）。比表面积及孔隙度、扫描电镜分析和X射线能谱分析结果表明,矿物质的添加增大了蚯蚓粪比表面积和孔容,改变了蚯蚓粪中矿物元素的占比。傅立叶变换红外光谱分析表明,矿物基蚯蚓粪中醇或羧酸类、芳香类以及多糖类物质增多,脂类和碳水化合物减少。X射线衍射分析表明,添加铁粉及磷矿粉制备出来的矿物基蚯蚓粪增加了磷酸盐、纳米零价铁等矿物组分。土壤培养和吸附解吸试验表明,施加矿物基蚯蚓粪显著提升了土壤对Cd的吸附强度,降低了对Cd的解吸率,其中以牛粪+20%铁粉+20%磷矿粉（VCFe+P）进行蚯蚓堆肥所获得的矿物基蚯蚓粪处理的土壤对Cd的吸附效果最佳,较施加纯蚯蚓粪的土壤吸附...     

On the mechanism of specific phosphate adsorption by hydroxylated mineral surfaces: A review

Abstract

The mechanism of specific phosphate adsorption by hydroxy‐lated mineral surfaces comprises two aspects: the phosphate‐hydroxyl surface reaction and the configuration of the adsorbed phosphate ion. Evidence pointing to ligand exchange as the mechanism of the phosphate‐surface hydroxyl reaction include kinetics of adsorption and desorption; hydroxyl ion release; infrared spectroscopy, and stereochemical calculations. Data pertaining to the coordination of adsorbed phosphate on hydroxy‐lated mineral surfaces have not been conclusive overall. Isotopic exchange experiments and studies of desorption kinetics do not provide definitive information on surface coordination. Measurements of hydroxyl ion release and crystallographic calculations provide support for the existence of both monodentate and bidentate surface complexes of phosphate ions. Infrared spectroscopic investigations suggest a binuclear complex on dried, phosphated goethite. However, these studies cannot be extrapolated automatically to soil minerals, since the addition of water favors formation of a monodentate surface complex. Further research is needed to establish the configuration of adsorbed phosphate ions.     

Adsorption of glycerophosphate on goethite (α‐FeOOH): A macroscopic and infrared spectroscopic study

Adsorption, desorption, and precipitation reactions at environmental interfaces govern the bioavailability, mobility, and fate of organic phosphates in terrestrial and aquatic environments. Glycerophosphate (GP) is a common environmental organic phosphate, however, surface adsorption reactions of GP on soil minerals have not been well understood. The adsorption characteristics of GP on goethite were studied using batch adsorption experiments, zeta (ζ) potential measurements, and in situ attenuated total reflectance‐Fourier transform infrared spectroscopy (ATR‐FTIR). GP exhibited fast initial adsorption kinetics on goethite, followed by a slow adsorption. The maximum adsorption densities of GP on goethite were 2.00, 1.95, and 1.44 μmol m^?2 at pH 3, 5, and 7, respectively. Batch experiments showed decreased adsorption of GP with increasing pH from 3 to 10. Zeta potential measurements showed a remarkable decrease in the goethite isoelectric point upon GP adsorption (from 9.2 to 5.5), suggesting the formation of inner‐sphere surface complexes. In addition, the ATR‐FTIR spectra of GP sorbed on goethite were different from those of free GP at various pH values. These results suggested that GP was bound to goethite through the phosphate group by forming inner‐sphere surface complexes.     

磷酸盐在水铁矿及水铁矿-胡敏酸复合体表面的吸附

The adsorption of phosphate onto ferrihydrite (FH) and two FH-humic acid (HA) complexes, obtained by co-precipitating FH with low (FH-HA1) and relatively high amounts of humic acid (FH-HA2), was studied through kinetics and isotherm experiments to determine the differences in phosphate adsorption between FH-HA complexes and FH and to reveal the mechanism of phosphate adsorption onto two soil compositions. The isoelectric point (IEP) and the specific surface area (SSA) of the mineral decreased as the particle porosity of the mineral increased, which corresponded to an increase in the amount of organic carbon. The adsorption capacity of phosphate was higher on FH than on FH-HA1 and FH-HA2 at the scale of micromoles per kilogram. The initial adsorption rate and adsorption affinity of phosphate decreased with an increase in the amount of HA in the mineral. The sensitivity of phosphate adsorption to the change in the pH was greater for FH than for FH-HA complexes. Ionic strength did not affect the adsorption of phosphate onto FH and FH-HA1 at a lower pH, and the increase in the ionic strength promoted phosphate adsorption at a higher pH. However, for the FH-HA2 complex, the increase in the ionic strength inhibited the adsorption of phosphate onto FH-HA2 at a lower pH and increased the adsorption at a higher pH.     

土壤矿物质吸附砷的研究进展

砷是一种有毒的重金属元素,由于自然和人为的原因,世界上的许多国家存在砷污染问题,因此有关砷污染的研究与控制日益受到人们的关注。本文介绍了土壤砷污染的产生原因及污染状况,重点集中在探讨土壤中的各种矿物质对砷吸附行为的作用机理。这些矿物质包括铁铝氧化物和氢氧化物、锰氧化物、黏土矿物和碳酸盐类。关于砷在各类矿物质上的吸附机理,普遍接受的观点认为:砷氧阴离子与矿物质的表面发生了配位体交换过程并通过共价键的作用,形成了表面配位体。表面配位体以内层双齿双核鳌合形式为主,受矿物质的种类、pH值和氧化还原电位等因素的影响,外层吸附和其他鳌合状态可能存在。砷在土壤矿物质上的吸附效果强烈依赖于体系的pH值,这与吸附的理论模型和数学计算结果相一致。矿物质的种类、组成、结晶状态和表面积等影响了砷的吸附过程和吸附效果。土壤中存在的各种阴阳离子通过与砷阴离子竞争吸附位而影响砷在矿物质上的吸附。     

凹凸棒石吸附铜离子的机理

A single-factor experiment of copper ion adsorption on pure palygorskite was carried out to understand the Cu^2 sorption of palygorskite-an important clay mineral in soil and sedimentary rock. In addition, pH of the solution and the surface microstructure of palygorskite were investigated before and after adsorption. The experimental results indicated that efficiency of Cu^2 removal was related to the oscillation rate of the specimen shaker, sorption time, initial pH value and the amount of adsorbent added. Palygorskite induced Cu^2 hydrolysis and interaction between copper hydroxide colloids and palygorskite surfaces, as observed with transmission electron microscopy (TEM), were the main contributions to palygorskite removal of Cu^2 . This mechanism was different from adsorption at the mineral-water interface. It was proposed that surface hydrolysis of palygorskite raised the alkalinity of the palygorskite-water interface and suspension system. Thus, the induced pH of the solution was then high enough for Cu^2 hydrolysis on the mineral surface and in solution.