Effects of Pb^2＋, Cd^2＋ and Cu^2＋ on the Aqueous Zn^2＋ Sorption by Hydroxyapatite

In this paper, the behaviors of aqueous zinc sorption by hydroxyapatite in the co-existence of Pb^2＋, Cd^2＋ and Cu^2＋ are investigated, the effects of Pb^2＋, Cd^2＋ and Cu^2＋ on the sorption of Zn^2＋ are discussed, and the hydroxyapatite sorption capabilities for Pb^2＋, Cd^2＋, Cu^2＋ and Zn^2＋ are compared. The experimental results show that the Zn^2＋ removal efficiency decreases gradually with the increase of the Cd^2＋ concentration of the solution, and there is no sorption preference between Cd^2＋ and Zn^2＋. On the other hand, the Zn^2＋ removal efficiency rapidly decreases rapidly with the increase of the Cu^2＋ concentration of the solution, and there is a clear sorption preference between Cu^2＋ and Zn^2＋. It is noticed that the Zn^2＋ removal efficiency is hardly changed with the variance of Pb^2＋ concentration because the removal mechanisms for these two ions are totally different. It is concluded that the adsorption affinities of the heavy metals for the hydroxyapatite follows this sequence： pb^2＋〉 Cu^2＋〉 Cd^2＋〉 Zn^2＋.     

羟基磷灰石吸附水溶液中Cd^2＋的影响因素的研究

对羟基磷灰石(Hap)固定水溶性Cd2+的影响因素进行了较为系统的实验研究.实验表明去除率与Cd2+初始浓度呈负相关,在Cd2+初始浓度<10 mg/L时,与作用时间、pH值、Hap用量呈正相关,温度对去除率的影响较小.通过正交实验确定了最佳吸附条件Hap用量为5 g/L,pH值为6,作用时间5 min.     

Removal of Lead, Copper, Zinc and Cadmium from Water Using Phosphate Rock

Removal of Pb2 ,Cu~(2 ),Zn~(2 )and Cd~(2 )from aqueous solutions by sorption on a natural phosphate rock(FAP)was investigated.The effects of the contact time and initial metal concentration were examined in the batch method.The percentage sorption of heavy metals from solution ranges generally between 50% and 99%.The amount of sorbed metal ions follows the order Cu>Pb>Cd>Zn. Heavy metal immobilization was attributed to both surface complexation of metal ions on the surface of FAP grains and partial dissolution and precipitation of a heavy metal-containing phosphate.The very low desorption ratio of heavy metals further supports the effectiveness of FAP as an alternative and low-cost material to remove toxic Pb~(2 ),Cu~(2 ),Zn~(2 )and Cd~(2 )from polluted waters.     

pH值对羟基磷灰石除镉行为的影响

介质的pH值是影响羟基磷灰石(Hap)除镉行为最为复杂的因素之一,它决定了水溶液中Cd2+的赋存状态及Hap的溶解特性与表面性质等,而这些因素与Hap的除镉行为密切相关。实验研究表明,强酸(pH<3)条件下Cd2+的去除率随pH值的升高增加较快,但当pH≥3时这种增加变缓。在广泛的pH值范围内,Hap在含镉溶液和空白溶液中均表现为质子催化和非化学计量比的溶解机理。根据络合平衡计算,Cd2+在不同pH值时具有不同的型体及分布系数。Hap在空白溶液中的表面电动电势ζ为负值,且随pH值的增加其电负性增大。由此可知Hap除镉行为的作用机理是表面络合与表面电位吸附,而不存在溶解 沉淀作用。     

Removal of Lead,Copper, Zinc and Cadmium from Water Using Phosphate Rock

Removal of Pb^2＋, Cu^2＋, Zn^2＋ and Cd^2＋ from aqueous solutions by sorption on a natural phosphate rock （FAP） was investigated. The effects of the contact time and initial metal concentration were examined in the batch method. The percentage sorption of heavy metals from solution ranges generally between 50% and 99%. The amount of sorbed metal ions follows the order Cu〉Pb〉Cd〉Zn. Heavy metal immobilization was attributed to both surface complexation of metal ions on the surface of FAP grains and partial dissolution and precipitation of a heavy metal-containing phosphate. The very low desorption ratio of heavy metals further supports the effectiveness of FAP as an alternative and low-cost material to remove toxic Pb^2＋, Cu^2＋, Zn^2＋ and Cd^2＋ from polluted waters.     

电容去离子化去除地下水中镉的影响因素

以高比表面积活性炭作为吸附剂制备电容电极,研究电容去离子化（CDI）对地下水中镉的吸附性能。分别探讨了镉初始质量浓度、体系供电电压、地下水中常见阳离子种类对CDI去除镉的影响。结果表明,CDI吸附镉符合准二级吸附动力学、满足Langmuir等温吸附方程,CDI对镉的吸附为单分子层吸附。吸附量随镉初始质量浓度的升高而增加;在低质量浓度时,较高的供电电压会提高初始阶段的吸附速率,但对电极的最终吸附量无显著影响;地下水中主要阳离子的存在增加了体系的电导率,从而促进了CDI对镉的吸附,提高了镉的吸附速率和去除率。     

天然斜发沸石吸附去除水中氨氮机理研究

采用天然斜发沸石吸附去除水中氨氮,利用X射线衍射(XRD)和X荧光光谱(XRF)分析沸石的物相组成和化学成分。通过批试验考察p H、氨氮初始浓度和温度对沸石吸附氨氮的影响,通过吸附等温线、吸附热力学和吸附动力学的研究探讨天然斜发沸石吸附氨氮的机理。溶液p H=8时沸石对氨氮的吸附效果最佳。Freundlich吸附等温线较Langmuir能更准确描述天然斜发沸石吸附氨氮的过程,该吸附过程属优惠吸附。对吸附热力学参数计算得到吉布斯自由能变ΔG~00,熵变ΔH~00,说明天然斜发沸石吸附氨氮是自发的吸热过程;熵变ΔS~00说明氨氮在沸石上的分布较在水溶液中的分布倾向无序。吸附动力学符合准二级动力学方程,且随着氨氮初始浓度的增大,吸附反应的优惠程度降低。运用颗粒内扩散模型对实验数据的拟合结果表明吸附过程分为两个阶段:前30分钟主要是外表面吸附,30分钟后主要是颗粒内扩散。     

Lead Removal from Aqueous Solution by Natural and Pretreated Zeolites

Hazardous metal cations enter water through the natural geochemical route or from the industrial wastes. Their separation and removal can be achieved by adsorptive accumulation of the cations on a suitable adsorbent. In the present work, toxic Pb(II) ions are removed from water by accumulating it on the surface of natural zeolite in three different forms; one untreated and two treated samples, one sample treated with 2 M HCI solution and other is treated with 3 M NaOH solution. Natural zeolite is mainly composed of clinoptilolite, and mordenite, with amount of non-zeolite phase (smectite and illite) and C and CT opal. The adsorption experiments are carried out using a batch process in environments of different pH, initial Pb(II) concentration, interaction time and amount of zeolites. Treated zeolite samples show high exchange capacity for Pb(II) compared to untreated sample, however, acid-treated sample shows an exceedingly good exchange capacity. Equilibrium data fitted well with the Langmuir isotherm model with maximum adsorption capacity of 115, 126, and 132 mg g⁻¹ of untreated natural zeolites, alkali-treated zeolites and acid-treated zeolites respectively. The rates of adsorption were found to confirm to pseudo-first order kinetic with good correlation and the overall rate of lead ions uptake.     

镉标准溶液配制结果的不确定度评定

选择氧化镉标准物质,配制成质量浓度为1000μg/mL的镉标准溶液,利用等离子体质谱法对标准溶液进行了定值与稳定性检验。通过对镉标准溶液配制过程不确定因素的描述,以95%概率下的扩展因子2获得标准溶液浓度配制标示值的扩展不确定度。实验数据表明,所配制的标准溶液稳定性可达2年。     

响应曲面法优化生物质炭去除水溶液中的阿特拉津

将农业废弃物大豆秆在450℃缺氧条件下热裂解制备生物质炭。采用元素分析仪、扫描电镜(SEM)、傅里叶变换红外光谱(FTIR)、光电子能谱分析(XPS)等手段对生物质炭进行理化性质分析;应用响应曲面法(RSM)下的中心合成设计(CCD)功能研究4个因素(初始pH、吸附剂质量浓度、阿特拉津质量浓度、温度)对阿特拉津去除率的影响;建立二阶模型,并通过方差分析验证二阶方程的有效性。结果表明:生物质炭表面充满孔状结构,且富含C=C、C-C、CHx、-C-OR、-COOR等官能团;吸附阿特拉津后生物质炭在羟基(-OH)的位置产生了新的吸收峰,推测羟基官能团在吸附过程中发挥了重要作用。RSM法优化最佳吸附去除阿特拉津条件为:初始阿特拉津质量浓度为5mg/L、pH=6.67,吸附剂质量浓度为7.75g/L、温度为32℃;在该条件下阿特拉津的吸附去除率达到92.18%。该研究可为评价施加生物质炭土壤中阿特拉津的迁移规律及阿特拉津污染水体修复提供参考。     

土壤对镉离子的竞争吸附研究——以北京城近郊为例

对分别采自北京城近郊丰台区北天堂村、大兴区庑殿村、通州区永乐店镇、海淀区四季青乡和朝阳区来广营乡5个典型地区的土壤进行了Cd^2＋-Na^＋、Cd^2＋-Ca^2＋、Cd^2＋-Zn^2＋双阳离子竞争性静态吸附试验。结果表明，在不改变土壤的物理化学性质条件下，多种离子共同竞争吸附时，其吸附过程与单个外源金属阳离子的吸附结果不同；不同类型土壤对镉的吸附受钠、钙、锌离子的影响不是单方面的抑制作用或促进作用，影响机制随着外源镉离子浓度和外源钠、钙、锌离子浓度的大小而各异，而且其影响程度也有所不同。     

冷蒸气发生-原子吸收光谱法测定日用陶瓷浸泡液中痕量镉

研究了冷蒸气发生-原子吸收光谱法测定日用陶瓷浸泡液中痕量镉的反应体系。对载气流速、NaBH4浓度、增敏剂加入量和介质酸度的影响,以及基体和共存离子的干扰进行了考察。将该方法与石墨炉原子吸收光谱法进行比较。方法简便快速,回收率为94.0%~104.9%,相对标准偏差(RSD,n=7)小于3.6%。方法具有快速、准确、灵敏度高、经济实用等优点,用于陶瓷浸泡液中痕量镉的测定,结果令人满意。     

断续流动在线分离富集-蒸气发生原子荧光光谱法测定复杂环境样品中痕量镉

用D201阴离子交换树脂富集样品中的痕量Cd，使Cd与共存干扰元素Cu、Ni、Pb、Zn有效分离，消除了这些元素对镉蒸气发生的干扰，从而建立了断续流动在线分离富集-蒸气发生原子荧光光谱法测定复杂环境样品中痕量Cd的分析方法。方法的检出限为3ng／L（3σ）；测定精密度（RSD）为1．9％（对1μg/L Cd，n=11）。用该方法对国家一级标准物质（土壤、水系沉积物和岩石）中的痕量镉进行了测定，结果与标准值相符。     

天然丝光沸石表面重构改性及其在水中去除重金属的应用

天然丝光沸石作为一种绿色廉价多孔材料广泛应用于环境治理中去除重金属,目前报道的天然沸石对重金属的去除率多在60%～90%,提升其去除效率已成为研究热点。本文采用正硅酸乙酯对天然丝光沸石进行表面重构改性,通过TEM、XRD、BET等手段表征其形貌和结构。结果表明:正硅酸乙酯水解生成的SiO_2可与天然丝光沸石复合形成新颖的"SiO_2/丝光沸石",原沸石表面包覆了新生纳米SiO_2孔结构,同时没有损坏原始沸石的多孔结构,使改性沸石材料兼具了天然丝光沸石和纳米SiO_2孔结构优点,增强了对重金属离子的吸附能力。该改性材料对水中Pb~(2+)、Cd~(2+)、Zn~(2+)和Mn~(2+)的最高吸附率为99. 3%、97. 1%、98. 3%和97. 0%,且极少解吸,性能稳定。考虑经济成本并保证合适吸附率的情况下选择吸附效率最佳的投加量,得到改性材料对初始浓度10 mg/L的Pb~(2+)、Cd~(2+)、Zn~(2+)、Mn~(2+)溶液的最佳投加量分别为0. 5 g/L、2 g/L、2 g/L、5 g/L,可为中试和规模应用提供参考。较之焙烧、酸、碱、盐和有机改性,本改性方式对多种重金属均有高的吸附率,并显现出操作简便、成本低和环境友好等优势,具有较好应用前景。     

Adsorption of Fe~(3+) Ions from Aqueous Solution by Natural and Synthetic Apatites: Kinetic,Equilibrium and Thermodynamic Study

In this study, the adsorption kinetics, equilibrium and thermodynamics of Fe3+ ions on natural (NAP) and synthetic (HAP) apaties were examined. The adsorption efficiency of Fe3+ onto the NAP and HAP was increased with increasing temperature. The kinetics of adsorption of Fe3+ ions was discussed using three kinetic models, the pseudo-first-order, the pseudo-second-order and the intra-particle diffusion model. The experimental data fitted very well the pseudo-second-order kinetic model. The initial sorption rate and the activation energy were also calculated. The activation energy of the sorption was calculated as 37.15 and 49.84 kJ·mol 1 for NAP and HAP, respectively. Experimental results were also analysed by the Langmuir, Freundlich and Dubinin–Redushkevich (D–R) isotherm equations at different temperatures. RL separation factor for Langmuir and the n value for Freundlich isotherm show that Fe3+ ions are favorably adsorbed by NAP and HAP. Various thermodynamic parameters such as enthalpy (ΔH), Gibbs free energy (ΔG) and entropy (ΔS) changes were computed and the results showed that the adsorption of Fe3+ ions onto NAP and HAP were spontaneous and endothermic in nature.     

Removal of Arsenic(V) from Aqueous Solutions by Lanthanum-loaded Zeolite

A new adsorption process for the removal of As（V） ion from aqueous solutions is studied in this paper using lanthanum-loaded zeolite. The removal efficiency of different adsorbents, activated alumina and activated carbon are obtained in the study for comparison. The results show that lanthanum-loaded zeolite is an effective adsorbent for the removal of As（V） from aqueous solutions. Then, the pH effect and regeneration of modified zeolite on the As（V） removing efficiency are also assessed. It functions with a wide range of pH （2-8）. After adsorption, zeolite adsorbed with As（V） ions can be regenerated successfully with 1 M NaOH. Based on the data obtained, an adsorption mechanism and the possible complex structure are tentatively presented. Compare to other adsorbents, easy availability of this adsorbent, excellent adsorption capacity, wide optimum pH range, and regeneration are expected to be utilized in practical operations.     

Heavy Metal Removal from Water by Adsorption Using Pillared Montmorillonite

Removal of Cu^2＋, Cr^3＋ and Cd^2＋ from aqueous solutions by adsorption on montmorillonite modified by sodium dodecylsulfate （SDS） and hydroxy-alumino-silicate （HAS） was investigated. Experiments were carried out as a function of solution pH, solute concentration, and time. The Langmuir model was adopted to describe the single-solute adsorption isotherm, in which the Langmuir parameters were directly taken from those obtained in single-solute systems. The kinetics of metal ions adsorption was examined and the pseudo-first-order rate constant was finally evaluated.     

北京城近郊区土壤对镉的吸附特征研究

在0．1～1200mg／L不同Cd^2＋浓度条件下，进行了五个地区土壤对重金属Cd^2＋的静态吸附实验。土壤分别采自于北京城近郊丰台区北天堂村、大兴区庑殿村、通州区永乐店镇、海淀区四季青乡和朝阳区来广营乡五个地区。实验结果表明：常温常压下，土壤对Cd^2＋的吸附量与加入到土壤中的Cd^2＋总量呈现出一定的正相关。四季青、永乐店的重粉质壤土、庑殿的中粉质壤土及北天堂的轻壤土对Cd^2＋的吸附量S与土壤溶液中的平衡浓度C都基本满足直线拟合。在相同外源Cd^2＋浓度下，土壤对Cd^2＋的吸附量为：庑殿的中粉质壤土〉四季青的重粉质壤土〉永乐店的重粉质壤土〉来广营的重粉质壤土〉北天堂的轻壤土。在所拟实验条件下，土壤对镉的吸附很大程度上受到土壤有机质含量、土壤的粘粒和粉粒所占比例的控制，而酸碱度pH和氧化还原电位Eh对类型不同的土壤的吸附影响效应不很明显。     

原子荧光光谱法测定铁矿石中的镉

样品经盐酸-硝酸-氢氟酸-高氯酸混合酸溶解,用原子荧光光谱法测定铁矿石中的镉。实验确定了最佳酸度、增感剂镍量、抗坏血酸量和硫脲量,并确定了仪器测定最佳条件,对干扰元素的允许量进行了研究。方法检出限为0.20μg/L,精密度为4.5%,线性范围为0~160μg/L,加标回收率为95.9%~103.7%。方法可应用于铁矿石的快速检测。     

天然锰钾矿吸附水溶液中Hg^2＋的实验研究

利用粉碎分级的天然锰钾矿去除水溶液中Hg^2 的实验研究表明：反应平衡时间约为20小时；pH值对其吸附率影响很大，在中性（氯化物在偏碱性）条件下吸附率较高；溶液中阳离子的存在会产生竞争吸附而降低对Hg^2 的吸附量，2价金属离子较1价金属离子对Hg^2 竞争干扰明显；溶液中Cl^-的存在能明显降低对Hg^2 的吸附量。对等温吸附曲线的回归分析得出在浓度为5～350mg/L段能很好地符合Langmuir单吸附位吸附曲线，并计算出在该实验条件下其最大理论吸附量为27.6mg/g。解吸实验结果表明，在无其他电解质参与的条件下解吸量较少，受多种电解质干扰时其解吸率不超过20%。