基于不同分析方法研究磷酸根在矿物表面吸附机制的进展

磷素是植物生长必需的营养元素,也是联系生态系统中生物与非生物作用的关键元素。对磷酸根在矿物表面吸附反应机制的深入认识,有助于了解其在陆地和水环境中的形态、迁移、转化和生物有效性。本文主要综述了磷酸根在常见(土壤)矿物表面吸附机制的研究进展。各种分析技术或方法,如OH–释放量分析、Zeta电位分析(电泳迁移率测试)、等温滴定量热法、原子力显微镜、X射线光电子能谱、红外光谱、核磁共振波谱、X射线吸收光谱、表面络合模型、量子化学计算等,均以不同方式揭示磷酸根在不同矿物体系的吸附机制。磷酸根在矿物(尤其是铁、铝氧化物)表面的吸附通常伴随着水基和羟基的交换。一般认为磷酸根在矿物表面主要形成双齿双核、单齿单核内圈络合物,且受pH的影响较大。pH以及磷酸根在矿物表面的吸附密度影响内圈络合物的质子化状态。在低pH、高磷浓度、较高反应温度、较长吸附时间,以及弱晶质矿物吸附等条件下矿物表面吸附的磷可在矿物表面转化形成含磷的表面沉淀,造成矿物溶解转化以及磷生物有效性的进一步降低。最后展望了磷酸盐在矿物-水界面吸附有关的研究热点和方向。     

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。     

砷镉在不同矿物界面的相互作用过程

重金属元素镉砷由于毒性高、活性大及危害强等特点,其土壤界面化学过程是土壤科学研究中的热点问题。虽然已有大量报道涉及镉砷的界面化学过程研究,但很少排除pH这一重要因子对研究结果的干扰。因此,本研究通过序批式反应,在排除pH干扰的条件下,定量研究了砷及镉在不同矿物界面（包括氧化铝、二氧化钛和高岭石）单独存在以及共同存在条件下的相互作用过程。研究结果表明：不同矿物界面上砷和镉的吸附动力学符合准二级动力学模型,化学吸附为其控速步骤;镉及砷的吸附效率（吸附量/比表面积）在不同矿物界面上均呈现出二氧化钛界面远高于氧化铝界面,而氧化铝界面高于高岭石界面;随着镉/砷浓度比的递增,镉的关键界面作用过程调控机制由静电吸附控制为主逐步转变为静电吸附与形成界面-砷-镉三元络合物共同作用,继而转变为形成表面沉淀控制;而随着砷/镉浓度比的递增,砷的关键界面调控机制发生从吸附控制为主向为沉淀控制为主的转变。该结果可为重金属元素在土壤矿物界面的微观化学作用过程及其调控措施研究提供借鉴。     

α-Fe2O3 对Cr(Ⅲ)的等温吸附特征研究

由于工农业生产中对铬的处理不力,造成土壤及地下水的严重污染。铬对人体的毒害能引起皮炎、湿疹、气管炎和鼻炎,并有致癌作用。重金属离子与土壤、矿物的相互作用是重金属环境地球化学循环的主要环节,而重金属在水体和土壤中的迁移转化过程主要表现为金属离子在矿物界面的吸附/解吸和沉淀作用[1]。矿物对重金属的吸附可以减轻或缓解环境污染。赤铁矿是一种重要的铁氧化物,是酸性土壤中广泛存在的稳定矿物之一,由于具有较大表面积、较多表面活性官能团以及较强的电荷可变性,使其对土壤的物理化学特性,尤其是对营养元素和污染物质、重金属离子的吸持、迁移、有效性和毒性均有着极其重要的作用。金属氧化物尤其是铁锰氧化物与重金属离子的     

α-Fe_2O_3对Cr(Ⅲ)的等温吸附特征研究

由于工农业生产中对铬的处理不力,造成土壤及地下水的严重污染.铬对人体的毒害能引起皮炎、湿疹、气管炎和鼻炎,并有致癌作用.重金属离子与土壤、矿物的相互作用是重金属环境地球化学循环的主要环节,而重金属在水体和土壤中的迁移转化过程主要表现为金属离子在矿物界面的吸附/解吸和沉淀作用.     

土壤腐殖质-矿物质交互作用的机制及研究进展

腐殖质、氧化物、层状硅酸盐矿物间的相互作用主要通过阴离子交换、配体表面交换、疏水作用、熵效应、氢键作用及阳离子桥键、静电作用等多种结合键能进行.影响有机-矿质复合体相互作用的主要因素是腐殖质、粘土矿物的性质及溶液pH值和离子强度等.矿物的比表面积、表面酸碱反应位、表面电荷以及腐殖酸的羧基、酚羟基、醇羟基、羰基、氨基等官能团含量和酸度、芳香性、干湿状况、分子大小等基本性质都会影响腐殖酸被矿物吸附的状况.矿物对腐殖酸的吸附量随着pH值的升高而降低,随着离子强度的增加而升高.本文针对土壤腐殖质、铁/铝氧化物、层状硅酸盐矿物相互作用的机制及其影响因素进行了综述.     

水分非饱和条件下土壤矿物界面有毒有机物转化机制研究进展

土壤矿物作为土壤重要活性组分，可驱动土壤有毒有机物化学转化，降低污染风险。以往土壤矿物与有毒有机物界面行为研究主要集中于水环境或矿物悬浊液体系，然而实际环境中土壤及其矿物常处于干燥、湿润等水分非饱和状态。近年来，水分非饱和条件下土壤矿物界面有毒有机物转化及机制已成为研究热点，相关研究获得一系列新发现。低含水量铁锰矿物、黏土矿物和金属离子饱和黏土矿物能驱动多环芳烃、抗生素等疏水性有毒有机物化学转化。水分非饱和环境会减弱矿物界面水分子与有毒有机物竞争活性位点，并使矿物发生脱水、向高活性结构转变。此外，土壤矿物水分状态也会影响有毒有机物转化产物，水分非饱和环境更有利于持久性自由基和卤代二噁英等中间产物的形成和稳定。以往研究认为，电子转移反应是土壤矿物界面有毒有机物转化机制，随着检测技术与理论计算的发展，自由基催化和水解作用机制逐渐被发现，相关机制研究精准至矿物晶型和晶面层面。虽然水分非饱和条件下土壤矿物界面有毒有机物转化及机制已逐渐清晰，但其研究广度和深度有待进一步拓宽和加深。建议未来在实际水分非饱和土壤和矿物中开展有毒有机物转化研究，深入探究还原转化过程，研发原位反应装置及检测方法，尝试从微纳米尺度和分子水平解析有毒有机物在矿物界面转化机制。     

土壤铁矿物的生物-非生物转化过程及其界面重金属反应机制的研究进展

铁矿物作为土壤的重要组成成分,一般可通过吸附、络合和共沉淀等方式影响重金属的生物有效性和毒性.此外,土壤中有机物的存在会影响铁矿物的转化,导致转化产物的结构和表面特性发生改变,进一步影响重金属的环境行为.本文从铁矿物、有机质和重金属等要素入手,综述了反应pH、温度、亚铁和微生物等因素影响下土壤铁矿物非生物和生物转化过程...     

金属离子在铁(氢)氧化物与腐殖质微界面上的吸附机理和模型研究进展

铁(氢)氧化物和腐殖质是广泛分布在土壤中的重要天然活性物质,因其具有较大的比表面积并且铁(氢)氧化物表面的-OH与腐殖质表面的-COOH、-OH等活性官能团可通过静电作用、配体交换等多种机制对重金属离子产生较强吸附,从而影响重金属离子在环境中的迁移、转化和生物效应。深入了解重金属离子在铁(氢)氧化物-腐殖质复合体微界面相互作用的分子机理,对于阐明重金属离子在环境中的迁移、转化过程具有重要意义。本文综述了金属离子在铁(氢)氧化物与腐殖质上吸附机理和模型的研究进展,为重金属污染土壤的风险评估和控制提供理论依据。     

α-氧化铝–细菌二元复合胶体对锑的吸附研究

锑(Sb)在土壤胶体微界面的吸附解吸深刻影响其迁移、转化和归趋。土壤矿物、有机物、微生物等胶体组分多结合在一起,形成复杂的矿物–有机复合体。目前,锑在单一土壤组分上的吸附研究颇多,但较少有学者关注锑在土壤矿物–有机复合胶体界面的吸附过程和机制。通过宏观吸附以及光谱学技术探究锑在典型铝氧化物–细菌复合胶体上的吸附行为,结果表明:α-Al_2O_3纳米级颗粒覆盖在蜡状芽孢杆菌表面,形成一层不完整的"矿物膜"。朗格缪尔(Langmuir)模型可以很好地拟合Sb(Ⅴ,Ⅲ)的等温吸附数据(R~20.98);α-Al_2O_3对Sb的吸附量远大于细菌;Sb在Al_2O_3–细菌复合胶体上的吸附不符合"组分相加"原则,存在显著的促进效应。扫描电镜-能谱分析显示Sb主要结合在复合胶体的矿物组分上。X-射线光电子能谱结果表明铝羟基、羧基和氨基参与了Sb的吸附,且细菌会抑制Sb(Ⅲ)在α-Al_2O_3表面的氧化。本研究证实,细菌不仅影响锑在矿物界面的吸附量,还影响其氧化还原反应,因此,在预测锑在土壤中的形态转化、迁移和归趋时必须考虑矿物–微生物相互作用。     

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...     

Sorption and desorption characteristics of organic phosphates of different structures on aluminium (oxyhydr)oxides

Sorption and desorption characteristics of four organic phosphates (OPs) with different molecular sizes and structures (glycerophosphate, GP; glucose‐6‐phosphate, G6P; adenosine triphosphate, ATP; myo‐inositol hexakisphosphate, IHP) and inorganic phosphate (P_i) on three aluminium (Al) (oxyhydr)oxides (amorphous Al(OH)₃, boehmite and α‐Al₂O₃) were investigated. The maximum sorption amounts of OPs and P_i increased with decreasing crystallinity of the minerals on a per mass basis: α‐Al₂O₃ < boehmite < amorphous Al(OH)₃. With an exception of IHP sorption on amorphous Al(OH)₃, the maximum surface area‐based sorption densities increased with decreasing molecular weight (MW) of OPs and P_i: IHP < ATP < G6P < GP < P_i. Despite having the largest MW, IHP had greater sorption amounts on amorphous Al(OH)₃ than the other OPs because of the transformation of surface complexes to surface precipitates. Sorption kinetics of OPs was first a rapid sorption followed by a long and slow sorption process. Of the three Al (oxyhydr)oxides, amorphous Al(OH)₃ had the greatest first rapid sorption density and initial sorption rate of OPs within 5 minutes, both factors decreasing with increasing MW of OPs. The initial desorption percentages of OPs by KCl generally increased with decreasing MW of OPs, whereas the maximum desorption percentages of OPs by citrate were four to five times those achieved with KCl. Overall, strong specific sorption of OPs occurs on the surface of Al (oxyhydr)oxides, and molecular structure and size of OPs, as well as crystallinity and crystal structure of the minerals, are the key factors affecting the interfacial reactions and environmental behaviour of OPs.     

除草剂草甘膦在几种土壤和矿物上的吸附研究

通过批平衡实验考察了草甘膦在几种性质不同土壤和矿物上的吸附行为。研究发现土壤对草甘膦有较强的吸附能力，草甘膦在土壤上吸附量的大小与土壤理化性质密切相关。草甘膦在土壤和矿物上的吸附符合Freundlich吸附方程，其在土壤上的吸附常数K与土壤粘粒含量呈正相关，并随土壤氧化铁和氧化铝含量增加而增加，而与土壤的pH呈显著负相关。草甘膦在高岭石上的吸附量要比在蒙脱石上大，而草甘膦在金属离子饱和的蒙脱石和高岭石上的吸附研究结果表明，草甘膦在钠、钙、铁离子饱和的矿物上的吸附能力依次为Fe-蒙脱石〉Ca-蒙脱石〉Na-蒙脱石和Fe-高岭石〉Ca-高岭石〉Na-高岭石。     

土壤矿物对有机质的吸附与固定机制研究进展

鉴于土壤有机质在生态系统及碳储存方面的重要性,关于土壤矿物对土壤有机质的吸附与固定机理方面的研究越来越受到了学术界的广泛关注。本文综述了近年来报道较多的土壤矿物对土壤有机质的吸附机制,以及主要影响因素。在众多矿物类型中,水合铁、铝氧化物及黏土矿物对有机质的吸附性较强,配体交换、络合、氢键、阳离子桥接、缩合及范德华力作用是土壤矿物与有机质之间的主要作用机制。土壤pH是影响矿物表面电荷及吸附位点的关键因素,进而影响矿物对有机质的吸附。土壤矿物表面的有机质含量对其继续吸附有机质具有一定的影响。吸附态有机质大多呈层状结构,越接近矿物表面的有机质与土壤矿物的结合越紧密。土壤有机质的稳定性受有机质与矿物间的作用力影响,一般而言,以化学键合吸附在矿物表面的有机质最稳定,其次为直接与矿物表面作用的电子"供体-受体"机制,范德华力和静电作用稳定性较差。近年来,随着分析设备和技术的进步,一些新的表征与探测方法(如热重分析、差示扫描量热法、傅里叶转换红外光谱、扫描电子显微镜、原子力显微镜、扫描透射X射线显微镜、中子散射技术等)被用于"矿物-有机质"结合机制的研究中,这些新手段毫无疑问会帮助更好地认识矿物与有机质间的作用机理。关于微生物在矿物吸附有机质、"矿物-有机质"复合体形成和演化过程中所起的作用,研究相对较少,但很明显这是至关重要的。     

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.     

铁铝氧化物–层状硅酸盐矿物互作对Cr (Ⅵ)和As (Ⅴ)吸附的影响

以高岭石、蒙脱土、针铁矿和三水铝石四种单一典型土壤矿物以及针铁矿-蒙脱石和三水铝石-蒙脱石（质量比为1:1）两种代表性土壤矿物复合体为吸附材料，采用吸附平衡实验、能谱分析（(EDS）、红外光谱、扫描电镜、酸碱滴定和zeta电位测定等方法，研究了铁铝氧化物与层状硅酸盐矿物之间的相互作用对Cr(Ⅵ)和As(Ⅴ)吸附的影响及其机制。吸附平衡实验和EDS实验结果表明，两种复合体对Cr(Ⅵ)和As(Ⅴ)的吸附容量均小于其两种组成矿物单一体系吸附量的平均值，即铁铝氧化物与蒙脱石的互作降低了这些氧化物对Cr(Ⅵ)和As(Ⅴ)的吸附能力。表面性质表征结果表明，与蒙脱石复合后，针铁矿与三水铝石表面的正电荷均被完全中和，电荷符号发生反转。与理论值相比，三水铝石-蒙脱石复合体的表面位点总浓度无明显变化，比表面积减小。针铁矿-蒙脱石复合体的比表面积与理论值无明显差异，但矿物表面位点浓度减小，表面羟基红外吸收峰强度减弱。氧化物与层状硅酸盐矿物互作改变了矿物表面性质，这可能是导致氧化物对Cr(Ⅵ)和As(Ⅴ)的吸附能力降低的主要原因。当评估污染元素在土壤中有效性时应当考虑土壤固相组分间的互作对离子吸附的影响。     

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.     

Interactive Sorption of Metal Ions and Humic Acids onto Mineral Particles

The sorption of metal ions (Pb2+, Zn2+ and Cu2+) and soil humic acids (HA) from aqueous solutions onto mineral particles (sand, calcite and clay) was investigated using a batch equilibrium system. The sorption reactions in two- component systems (heavy metals-mineral particles and humic acids- mineral particles), as well as interactions in three-component system (heavy metals-humic acids-mineral particles) were examined. Results showed that the presence of humic acids, dissolved or bound onto mineral surfaces, considerably influenced the fixation of heavy metals. The various effects, depending on mineral type, humic concentration and specific metal-ion, were observed in three- component system. Sorption of Cu2+-ions on all minerals studied rapidly increased as the concentration of dissolved HA increased. The amount of Pb2+-ions sorbed on sand slightly decreased, while on kaolin increased between 15 and 20%. Sorption of Zn2+-ions on all minerals studied decreased at pH 4. At pH 5.5 the sorption of Zn2+-ions onto calcite decreased, while on kaolin and sand increased as a function of the humic acid concentration giving the curve with maximum at c(HA) = 2.5 mmol C L-1. At pH 6.5 sorption onto kaolin and sand increased. This effect occurs as a result of the conditional stability constant of Zn-HA complexes increasing at higher pH which in turn promotes the chelation of Zn2+-ions to mineral- bound humic substances. The enhanced sorption of metal ions from the aqueous phase in three-component systems is not only the result of mineral sorption of free metals but also the result of chelation with HA sorbed on the mineral surface.