ATR-FTIR and XPS study on the structure of complexes formed upon the adsorption of simple organic acids on aluminum hydroxide

Information on the binding of organic ligands to metal （hydr）oxide surfaces is useful for understanding the adsorption behaviour of natural organic matter on metal （hydr）oxide. In this study, benzoate and salicylate were employed as the model organic ligands and aluminum hydroxide as the metal hydroxide. The attenuated total reflectance Fourier transform infrared （ATR-FTIR） spectra revealed that the ligands benzoate and salicylate do coordinate directly with the surface of hydrous aluminum hydroxide, thereby forming innersphere surface complexes. It is concluded that when the initial pH is acidic or neutral, monodentate and bridging complexes are to be formed between benzoate and aluminum hydroxide while bridging complexes predominate when the initial pH is alkalic. Monodentate and bridging complexes can be formed at pH 5 while precipitate and bridging complexes are formed at pH 7 when salicylate anions are adsorbed on aluminum hydroxide. The X-ray photoelectron （XP） spectra demonstrated the variation of C 1 s binding energy in the salicyate and phenolic groups before and after adsorption. It implied that the benzoate ligands are adsorbed through the complexation between carboxylate moieties and the aluminum hydroxide surface, while both carboxylate group and phenolic group are involved in the complexation reaction when salicylate is adsorbed onto aluminum hydroxide. The information offered by the XPS confirmed the findings obtained with ATR-FTIR.     

可变电荷表面对磷的吸附与解吸动力学

研究了可变电荷表面为主的土壤对磷的吸附与解吸动力学。结果麦明,磷吸附和解吸动力学均可用修正的Elovich方程、双常数速率方程和分段拟合的抛物线扩散公式来表征。吸附和解吸过程均可分为快、慢两个反应阶段。磷吸附过程是一个扩散控制的不可逆过程.     

滇池表层沉积物对磷的吸附特征

在室内模拟条件下,从滇池表层沉积物对磷的吸附动力学与热力学两个角度出发,研究了滇池沉积物对磷的吸附特征,同时探讨了不同磷形态对磷吸附特性的影响,结果表明:1滇池不同形态磷含量顺序为:有机磷钙(O-P)钙结合态磷(Ca-P)金属氧化物结合态磷(Al-P)残渣态磷(Res-P)可还原态磷(Fe-P)弱吸附态磷(NH4Cl-P);2沉积物对磷的吸附动力学过程分为2个阶段,即快吸附和慢吸附阶段.快吸附阶段主要发生在0~0.5 h内,而慢吸附阶段主要发生在0.5~4 h.滇池沉积物对磷的吸附过程主要在4 h内完成.3外海北部上覆水磷酸盐(SRP)浓度低于沉积物中磷的吸附/解吸平衡浓度(EPC0),可初步判断该区域沉积物有向上覆水体释放磷的风险.4不同区域沉积物磷的最大吸附量(Qmax)和总最大吸附量(TQmax)均以外海南部最大.5沉积物本底吸附态磷含量(NAP)与钙结合态磷(Ca-P)呈显著正相关关系(R2=0.5139,p0.05),而其他吸附特征参数与磷形态之间相关性均不显著.6与洱海、太湖等湖泊相比,滇池沉积物磷的本底吸附态磷(NAP)和最大吸附量(Qmax)均处于较高水平,磷污染较为严重.     

Enhanced phosphate removal using zirconium hydroxide encapsulated in quaternized cellulose

Zirconium-based materials are efficient adsorbent for aqueous phosphate removal. However, current zirconium-based materials still show unsatisfied performance on adsorption capacity and selectivity. Here, we demonstrate a zirconium hydroxide encapsulated in quaternized cellulose (QC–Zr) for the selective phosphate removal. Zirconium hydroxide nanoparticles were simultaneously generated in situ with the QC framework and firmly anchored in the three-dimensional (3D) cross-linked cellulose chains. The maximum P adsorption capacity of QC–Zr was 83.6 mg P/g. Furthermore, the QC–Zr shows high P adsorption performance in a wide pH range, generally due to the electrostatic effects of quaternized cellulose. The enhanced adsorption of P was also achieved in the presence of competing anions (including Cl^?, NO₃^?, ${\text{SO}}_4^{2?}$, ${\text{SO}}_4^{\mathrm{4}?}$) and humic acid (HA) even at a molar ratio up to 20 levels. The column adsorption capacity of QC–Zr reached 4000 bed volumes (BV) at EBCT = 0.5 min as the P concentration decreased from 2.5 to 0.5 mg/L. Mechanism study revealed that both –N⁺(CH₃)₃ groups and zirconium hydroxide were involved in phosphate adsorption via electrostatic interactions between –N⁺(CH₃)₃ and phosphate, and the formation of zirconium hydrogen phosphate (Zr(HPO₄)x). The ³¹P nuclear magnetic resonance (NMR) study implied that P surface–precipitated and inner–sphere complexed with zirconium hydroxide at a ratio of 3:1.     

洱海表层沉积物吸附磷特征

试验研究了洱海表层沉积物吸附磷动力学与等温吸附过程,探讨了总有机质与总钙对沉积物吸附磷参数的影响. 结果表明:①洱海表层沉积物对磷的吸附动力学过程均可分为2个阶段,即快速吸附阶段和慢速吸附阶段. 快速吸附阶段主要发生在0～0.5 h内,而慢速吸附阶段主要发生在0.5～5 h,所有沉积物均在5 h内基本达到吸附平衡. ②不同采样点沉积物对磷的Q_max(最大吸附容量,为904.60～1 420.34 mg/kg)及MBC(最大缓冲容量,为477.33～2 300.95 L/kg)均以西岸沉积物明显高于东岸,但其EPC₀(吸附-解吸平衡浓度,为0.015～0.068 mg/L)则相反. ③沉积物总有机质和总钙含量与其Q_max和V_max(最大吸附速率)呈显著正相关,但与EPC₀呈显著负相关. ④洱海表层沉积物吸附磷参数V_max和Q_max明显高于长江中下游浅水湖泊沉积物,而参数EPC₀较低. 因此,洱海沉积物释放风险较大但现今释放量较小,与洱海沉积物总有机质和总钙含量较高有关.      

Friedel层状化合物对正磷酸根的去除效应及其作用机制

为了解Friedel化合物除磷的应用潜能,研究了Friedel化合物对正磷酸根的吸附动力学和吸附等温线,并结合反应后溶液中各离子浓度的变化和反应固相产物的XRD、红外光谱分析,探讨其除磷作用机理.结果表明:Friedel化合物对正磷酸根的吸附等温线符合Langmuir等温吸附方程,理论吸附容量为4.86mmol·g-1;Friedel化合物除磷作用机理主要为溶出钙离子的沉淀作用,同时存在氢氧化铝的固磷作用.     

恩诺沙星在含水氧化铝和含水氧化铁上的配位吸附及配位增溶效应

采用批平衡试验方法,研究了恩诺沙星(ENR)在含水氧化铝(HAO)和含水氧化铁(HFO)上的吸附行为.结果表明,恩诺沙星在两类不同含水氧化物上的吸附可以用Langmuir等温方程描述,其中,吸附平衡常数K_L (HFO) > K_L (HAO).当溶液中NaCl的浓度在0.01~0.50 mol·L^-1之间时,恩诺沙星的最大吸附量随着溶液离子强度的增大呈下降趋势,但吸附低浓度的恩诺沙星时,离子强度对吸附量的影响不大,表明此时两类含水氧化物对恩诺沙星的吸附均以配位反应为主.实验还发现,在较强的酸性或碱性环境中,恩诺沙星的吸附量都明显减小,配位吸附主要发生在pH为5~8的范围内,配位点主要发生在C-3羧基的位点上,形成ENR∶M (金属离子) =1∶1型的配合物,同时生成的表面配合物促进了恩诺沙星的溶解.     

粉末活性焦对水中磷酸盐的吸附性能

以蒙东褐煤为原料,通过沉降炉炭化活化一步法制备了粉末活性焦（COKE）,其具有丰富的孔隙结构,以微孔为主,占据比表面积的79.3%.考察了活性焦对水中磷酸盐的吸附性能,并进一步研究了吸附时间、温度、初始pH值、初始磷酸盐浓度、活性焦投加量和共存离子对吸附过程的影响,以及吸附动力学、吸附等温线和热力学特征.结果表明：活性焦对水体中的磷酸盐具有良好的吸附性能.在30℃,pH=7的条件下,利用20.00g/L活性焦吸附1mg/L磷酸盐溶液,60min即可达到吸附平衡,此时吸附率可达89.4%.当吸附温度越高（10~40℃）,活性焦投加量越大,溶液pH值在6~7时,活性焦对水中磷酸盐的去除效果越好.共存离子的存在（NO₃^-、SO₄^2-、CO₃^2-）对活性焦吸附磷酸盐有抑制作用.活性焦对磷酸盐溶液的吸附过程较好符合Freundlich模型（R²>0.99）和准二级动力学模型（R²>0.99）,最大吸附容量为1.746mg/g（30℃）,并通过热力学分析发现此过程为自发的吸热反应.利用傅立叶红外光谱分析进一步表明,活性焦吸附磷酸盐主要依靠配位交换.与活性炭相比,活性焦性价比更高,具有良好的应用前景.     

Removal of trace arsenic（V） and phosphate from water by a highly selective ligand exchange adsorbent

The ligand exchange adsorbent could be used to remove the toxic arsenic(V) and phosphate efficiently from water even in the presence of foreign anions and possible to apply in chemical industry.     

Removal of phosphate by Fe-coordinated amino-functionalized 3D mesoporous silicates hybrid materials

Phosphate removal from aqueous waste streams is an important approach to control the eutrophication downstream bodies of water. A Fe(III) coordinated amino-functionalized silicate adsorbent for phosphate adsorption was synthesized by a post-grafting and metal cation incorporation process. The surface structure of the adsorbent was characterized by X-ray di raction, N2 adsoropion/desoprotion technique, and Fourier transform infrared spectroscopy. The experimental results showed that the adsorption equilibrium data were well fitted to the Langmuir equation. The maximum adsorption capacity of the modified silicate material was 51.8 mg/g. The kinetic data from the adsorption of phosphate were fitted to pseudo second-order model. The phosphate adsorption was highly pH dependent and the relatively high removal of phosphate fell within the pH range 3.0–6.0. The coexistence of other anions in solutions has an adverse e ect on phosphate adsorption; a decrease in adsorption capacity followed the order of exogenous anions: F?? > SO2?? 4 > NO??3 > Cl??. In addition, the adsorbed phosphate could be desorbed by NaOH solutions. This silicate adsorbent with a large adsorption capacity and relatively high selectivity could be utilized for the removal of phosphate from aqueous waste streams or in aquatic environment.     

活性氧化铝对水中磷的去除与回收研究

使用活性氧化铝作为吸附剂研究其对磷的吸附特性,并对不同提取剂对磷的回收效果进行了讨论.结果表明,活性氧化铝对使用蒸馏水、自来水及洱海入湖河流罗时江水配制的磷溶液有不同的磷吸附效果,其对3种不同磷溶液的吸附等温线模型均符合Langmuir模型,经计算得到理论最大吸附量分别为20.88、32.15和29.85 mg·g-1.通过吸附试验表明,电解质的存在对吸附效果有促进作用.pH值越低,活性氧化铝表面的Zeta电位越高,越有利于磷吸附.对比使用4种不同提取剂的试验结果表明,使用0.1 mol·L-1NaOH基本可以完全提取活性氧化铝吸附的磷.     

洱海河口湿地沉积物对磷的吸附特征及影响因素

为探明洱海入湖河口湿地沉积物对磷的截留效应,采集干、湿季罗时江湿地沉积物,通过吸附动力学、吸附等温线试验并结合吸附模型拟合,分析沉积物对磷吸附快慢和强弱的时空特征,结合沉积物基本理化指标讨论主导吸附机制和影响因素.结果表明:罗时江湿地表层沉积物对磷快吸附阶段的速率常数较慢吸附阶段高1个数量级,最大吸附速率[85.1 mg/（kg·h）]在30 min内达到,吸附速率及磷在颗粒物内部的扩散速率均表现为干季高于湿季;低磷起始浓度下测得沉积物吸附-解吸平衡浓度（EPC₀）为（0.037±0.010）mg/L,相比其他湖泊而言处于中等偏低水平;高磷起始浓度沉积物对磷的最大缓冲容量（MBC）呈干季高于湿季、底层高于表层、湿地内部采样点高于入口和出口的趋势;Dubinin-Radushkevich等温吸附模型计算得到吸附能范围为8.65~12.79 kJ/mol,吸附作用性质为离子交换;沉积物矿物元素Fe、Al的相对含量与吸附特征参数呈显著正相关.研究显示,罗时江湿地沉积物矿物元素Fe、Al的相对含量是该区域沉积物磷吸附动力学和热力学时空差异的主导因素.      

Effects of phosphate on the adsorption of glyphosate on three different types of Chinese soils

Glyphosate （GPS） is a non-selective, post-mergence herbicide that is widely used throughout the world. Due to the similar molecular structures of glyphosate and phosphate, adsorption of glyphosate on soil is easily affected by coexisting phosphate, especially when phosphate is applied at a significant rate in farmland. This paper studied the effects of phosphate on the adsorption of glyphosate on three different types of Chinese soils including two variable charge soils and one permanent charge soil. The results indicated that Freundlich equations used to simulate glyphosate adsorption isotherms gave high correlation coefficients（0.990-0.998） with K values of 2751, 2451 and 166 for the zhuanhong soil（ZH soil, Laterite）, red soil（ RS, Udic Ferrisol） and Wushan paddy soil（WS soil, Anthrosol）, respectively. The more the soil iron and aluminum oxides and clay contained, the more glyphosate adsorbed. The presence of phosphate significantly decreased the adsorption of glyphosate to the soils by competing with glyphosate for adsorption sites of soils. Meanwhile, the effects of phosphate on adsorption of glyphosate on the two variable charge soils were more significant than that on the permanent charge soil. When phosphate and glyphosate were added in the soils in different orders, the adsorption quantities of glyphosate on the soils were different, which followed GPS-soil 〉 GPS-P-soil = GPS-Soil-P 〉 P-soil-GPS, meaning a complex interaction occurred among glyphosate, phosphate and the soils.     

磷酸根和镉离子在羟基铁改性膨润土表面的协同吸附机制研究

聚合羟基金属-粘土矿物复合物广泛存在于自然环境中,对重金属阳离子和含氧酸根阴离子均有很好的吸附能力,因此对这些化合物的环境迁移过程及污染控制具有重要影响.研究采用FeCl₃和Na₂CO₃共同改性膨润土,制备了羟基铁－膨润土复合物（HyFe-Bent）.XRD和孔结构分析结果发现,HyFe-Bent的d₀₀₁由原土的1.52 nm增加到1.81 nm,比表面积由原土的52.2 m²·g^-1增大到108.4 m²·g^-1.将HyFe-Bent用于同时吸附水中磷酸根（P）和镉离子（Cd）,结果表明,在实验条件下P和Cd在HyFe-Bent上表现出明显的协同吸附效应,溶液pH升高可促进Cd的吸附但降低P的吸附.此外研究了P和Cd吸附次序对它们吸附性能的影响：在先吸附P的体系中两种物质的吸附性能与同时吸附体系相当,而在先吸附Cd的体系中吸附性能则明显低于同时吸附体系.由此提出P和Cd协同吸附的原理是多种吸附机制共存：除了配体交换和离子交换作用,它们在HyFe-Bent表面还发生了表面沉淀作用,可能形成了Fe-P-Cd三元络合产物.论文研究结果可为了解重金属和含氧酸根复合体系的环境行为及污染控制提供新信息.     

腐殖酸对针铁矿吸附磷的影响机理

通过添加HA(Humic acid,腐殖酸),研究不同环境条件下HA对针铁矿吸附磷的影响. 结果显示,加入HA能显著降低磷吸附量,pH为4.5时分别加入100和40 mg/L HA,磷的最大吸附量分别降低了26.6%和25.6%;pH为7.0时分别加入100和40 mg/L HA,磷的最大吸附量分别降低了26.8%和23.1%. 不同添加顺序试验结果表明:针铁矿对磷的吸附量大小顺序为后添加HA>同时添加HA和磷>先添加HA;无论是否添加HA,针铁矿对磷的吸附量都随着pH的升高而降低,相应的吸附等温线也都符合Langmuir吸附等温方程;总有机碳和红外光谱特征表明,HA和磷在针铁矿表面吸附点位形成竞争吸附,并且针铁矿表面的羟基在吸附磷和HA的过程中起到了一定的作用.      

锆-十六烷基三甲基氯化铵改性活性炭对水中硝酸盐和磷酸盐的吸附特性

采用锆(Zr)和阳离子表面活性剂十六烷基三甲基氯化铵(CTAC)对活性炭进行联合改性,考察了所制备的Zr-CTAC改性活性炭对水中硝酸盐和磷酸盐的吸附去除作用,并探讨了相关的吸附去除机制.结果表明,Zr-CTAC改性活性炭对水中硝酸盐和磷酸盐均具备较好的吸附去除能力.Zr-CTAC改性活性炭对硝酸盐和磷酸盐吸附动力学过程满足准二级动力学模型.Langmuir、Freundlich和Dubinin-Radushkevich(D-R)等温吸附模型可以较好地描述Zr-CTAC改性活性炭对水中硝酸盐的等温吸附过程,Langmuir和D-R等温吸附模型可以较好地描述Zr-CTAC改性活性炭对水中磷酸盐等温吸附过程,通过Langmuir模型计算得到吸附剂对硝酸盐和磷酸盐的最大单位吸附量分别为7.58 mg·g-1和10.9 mg·g-1.高的p H会抑制Zr-CTAC改性活性炭对水中硝酸盐和磷酸盐的吸附.水中共存的Cl-、HCO-3和SO2-4等阴离子均会抑制Zr-CTAC改性活性炭对硝酸盐和磷酸盐的吸附,且对吸附硝酸盐的抑制作用较强而对吸附磷酸盐的抑制作用较弱.水中共存的磷酸盐对Zr-CTAC改性活性炭吸附硝酸盐的抑制作用较强,而水中共存的硝酸盐对Zr-CTAC改性活性炭吸附磷酸盐的抑制作用较弱.1 mol·L-1Na Cl溶液可以使90%左右被吸附到Zr-CTAC改性活性炭表面上的硝酸盐解吸下来.1 mol·L-1的Na OH溶液可以使78%左右被吸附到Zr-CTAC改性活性炭表面上的磷酸盐解吸下来.Zr-CTAC改性活性炭对硝酸盐的吸附机制主要包括阴离子交换作用和静电吸引作用,对磷酸盐的吸附机制主要包括配位体交换作用、阴离子交换作用和静电吸引作用.上述结果说明Zr-CTAC改性活性炭适合作为一种吸附剂去除废水中的硝酸盐和磷酸盐.     

pH和有机酸对氟溶出砖红壤中铝离子的影响

研究砖红壤对F-的吸附反应尤其是随后Al3+的释放过程,有助于增进对土壤酸化过程及其环境影响的理解. 在初步揭示出F-吸附反应以及Al3+释放反应的动力学特征基础上,重点考察了pH和有机酸对上述反应的影响. 结果表明:土壤对F-的吸附反应十分迅速,2 min内吸附量即可达到24 h内总吸附量95%,而土壤中不同含铝矿物的溶解度差异使Al3+的释放过程在前15 min十分迅速,释放量可达24 h内总释放量的80%,随后则逐渐减缓. 降低反应体系pH可促进Al3+释放,但会使F-吸附量减少,这是因为伴随Al3+的释放,部分F-又可以AlF络合物的形态重新进入溶液,尽管在低pH条件下,土壤表面以带正电荷为主而有利于F-吸附. 草酸和抗坏血酸对土壤吸附F-均有抑制作用,但对F-溶出土壤Al3+有促进作用. 此外,草酸对土壤铁氧化物的选择性溶解作用,可使更多F-吸附在土壤铝氧化物位点,并导致Al3+释放量增加.      

氢氧化镧改性介孔稻壳生物炭除磷性能

通过共沉淀法将氢氧化镧固定在高介孔率的稻壳生物炭上,重点研究了生物炭孔结构、溶液pH和共存物质对氢氧化镧改性介孔稻壳生物炭吸附磷酸盐的影响.结果表明,镧负载量与生物炭介孔率呈正相关,生物炭介孔率越高,对磷酸盐的吸附速率越快,镧浸出量越低.吸附过程符合伪二级动力学模型,且受颗粒内扩散控制.Langmuir模型能够较好地描述氢氧化镧改性介孔稻壳生物炭对磷酸盐的吸附过程,理论最大吸附量分别为41.22、43.26和45.62 mg·g^-1,镧利用率较高,P/La量比均大于1.5.此外,氢氧化镧改性介孔稻壳生物炭能在pH 3~9的范围内有效吸附磷酸盐.共存物质影响实验表明,氢氧化镧改性介孔稻壳生物炭对磷酸盐表现出良好的选择吸附性,共存Ca²⁺会强化其对磷酸盐的吸附,而共存Mg²⁺则会抑制吸附过程.     

A model and experimental study of phosphate uptake kinetics in algae: Considering surface adsorption and P-stress

Phosphorus is an important limiting nutrient in many ecosystems. Consequently, there is increasing interest on phosphate uptake and algal growth due to the increasing frequency and magnitude of algal blooms induced by eutrophication. The co-existence of surface adsorbed and intracellular phosphorus pools indicate that phosphate uptake by phytoplankton is, to some extent, a two-stage kinetic process. However, almost all previous uptake models considered the internal uptake stage only and ignored the possible impact of surface adsoption. In this article, a two-stage kinetic uptake model considering both surface adsorption and P-stress on phosphate uptake by algae was constructed and compared to conventional one-stage models, based on experimental data on short-term uptake kinetics of a green algae S. quadricauda. Results indicated that with suitable parameters, the two-stage uptake model not only fit the experimental data better, but also gave more reasonable and realistic explanations to the phosphate uptake process. The results are meaningful as surface-adsorption of phosphate may a ect the uptake process of phosphate and assist in understanding realistic phosphate uptake kinetics in phytoplankton.     

不同锆负载量锆改性膨润土对水中磷酸盐吸附作用的对比

通过实验对比考察了不同锆负载量的锆改性膨润土对水中磷酸盐的吸附作用.结果表明,锆改性膨润土对水中磷酸盐的吸附动力学过程符合准二级动力学模型,整个过程可以分为快速吸附阶段、缓慢吸附阶段和平衡吸附阶段,其中缓慢吸附阶段的吸附速率受膜扩散和颗粒内扩散所控制.锆改性膨润土对水中磷酸盐的吸附等温实验数据可以采用Langmuir、Freundlich、Sips和Dubinin-Radushkevich等温吸附模型进行拟合.实验条件下,磷酸盐吸附性能随pH增加而降低.溶液共存的Na~+、K~+和Ca~(2+)促进了锆改性膨润土对磷酸盐的吸附,并且Ca~(2+)的促进作用远远大于Na~+和K+,而溶液共存的HCO-3和SO2-4一定程度上抑制了锆改性膨润土对磷酸盐的吸附.锆改性膨润土吸附水中磷酸盐的主要机制为配位体交换并形成内层磷酸盐配合物.锆改性膨润土对水中磷酸盐的吸附能力随着锆负载量的增加而增加,而锆改性膨润土中单位质量ZrO_2对水中磷酸盐的吸附量则随着锆负载量的增加而降低.当ZrO_2负载量由3.61%增加到13.15%时锆改性膨润土的最大单层单位吸附量(以P计)显著地由3.83 mg·g~(-1)增加到9.03 mg·g~(-1),而继续增加ZrO_2负载量至19.63%时锆改性膨润土的最大单层单位吸附量则缓慢地提高到9.66 mg·g~(-1)(以P计).当ZrO_2负载量由3.61%逐渐增加到19.63%时,锆改性膨润土中单位质量ZrO_2的磷酸盐最大吸附量[m(P)/m(ZrO_2)]由106 mg·g~(-1)逐渐下降到49.2 mg·g~(-1).综合考虑吸附剂的经济成本和吸附容量,ZrO_2负载量为13.15%锆改性膨润土更为适合作为吸附剂去除水中磷酸盐.