重金属离子在胡敏酸-高岭石复合体上的吸附

本文研究了胡敏酸存在下高岭石对重金属离子的吸附行为。实验结果表明:①胡敏酸和Cu2 溶液按先后顺序或同时加入高岭石中反应,在Cu2 平衡浓度<10mg/L时,3种加入顺序对Cu2 的吸附量基本相同,当Cu2 平衡浓度>10mg/L时,(K Cu) HA和(K Cu HA)两种加入顺序对Cu2 的吸附量比(K HA) Cu的略大。②在pH=5时,胡敏酸-高岭石复合体对Cu2 的吸附量明显大于纯高岭石。这是由于胡敏酸含有大量的羧基和酚羟基等活性基团,吸附在高岭石上的胡敏酸增加了其表面吸附位,在复合体表面形成了S—HA—Cu三元配合物,且Cu2 的吸附量与复合体中胡敏酸的含量在一定范围内成正相关;③溶液pH值在4～7之间变化可调控复合体对Cu2 的吸附机制。④在Cu2 和Cd2 共存时,随着金属离子初始浓度的增大,Cu2 的吸附量呈直线上升,而Cd2 的吸附量增加缓慢,表明复合体对Cu2 的吸附能力比对Cd2 强。     

矿物-腐植酸-微生物体系对重金属吸附研究

设施农业中土壤重金属污染问题日趋严重。由于土壤中矿物、腐植酸、微生物等多相组分之间存在交互作用,重金属与土壤单组分体系中所获得的结合机制并不能真实有效地评价其在自然条件下的转化与归趋。本研究以蒙脱石(Mont)和高岭石(Kao)为辽宁蔬菜大棚及农田土壤层状硅酸盐代表矿物,选取胡敏酸(HA)为有机质代表,土著微生物革兰氏阳性枯草芽孢杆菌(Bacillus subtilis,B.s)、革兰氏阴性恶臭假单胞菌(Pseudomonas putida,P.p)为细菌微生物代表,以此三元体系为主要供试蔬菜大棚土壤组分,以Cd~(2+)、Cu~(2+)为目标元素,借助宏观吸附实验,结合X射线衍射(XRD)、衰减全反射-傅立叶变换红外光谱(ATR-FTIR)、扫描电镜(SEM)测试分析了Cd~(2+)、Cu~(2+)在矿物-腐植酸-细菌三元混合物上的吸附机理以及Cd~(2+)、Cu~(2+)在复合体上的结合机制。研究结果表明,蒙脱石/高岭石-腐殖酸、蒙脱石/高岭石-B.s及蒙脱石/高岭石-P.p二元复合体对Cd~(2+)及Cu~(2+)的吸附具有加和性,矿物-腐植酸-微生物三元复合体之间表现为拮抗作用。吸附动力学研究表明矿物、有机质、微生物复合体对重金属的吸附动力学符合准二级动力学模型。体系对Cu~(2+)的吸附能力由强到弱为:B. s P. p Mont/Kao-B. s Mont/Kao-P. p Mont/KaoHA-P.p Mont/Kao-HA Mont/Kao。     

腐植酸改性强化磁铁矿吸附水体中铅镉的实验研究

磁铁矿是一种绿色廉价的矿物材料,对水体中重金属离子具有良好的吸附性,但吸附容量低,选择性差,易团聚,通过改性可以克服该缺点并提高其吸附性能。本文以腐植酸为改性剂,采用常温水相反应制备了腐植酸改性磁铁矿吸附材料。通过傅里叶红外光谱(FTIR)、扫描电镜(SEM)和X射线光电子能谱(XPS)表征研究其表面形貌和微观结构。采用静态平衡实验考察了pH、吸附时间等因素对铅、镉吸附性能的影响,探讨了吸附动力学规律,拟合了吸附等温线。结果表明:腐植酸上的羧基、羟基被成功地接枝到了磁铁矿表面。在室温下,溶液初始pH对Pb~(2+)的吸附率几乎无影响,对Cd~(2+)的影响较大,当pH=7时,Pb~(2+)和Cd~(2+)吸附率均达到了95%。对初始质量浓度为10mg/L的Pb~(2+)、Cd~(2+)最佳吸附平衡时间为360min,吸附过程符合准二级动力学方程。吸附等温线实验得到的竞争吸附顺序为Pb~(2+)Cd~(2+),由Langmuir等温吸附模型得到Pb~(2+)、Cd~(2+)饱和吸附容量分别为39.27mg/g、28.95mg/g,显著大于磁铁矿的饱和吸附容量,表明磁铁矿经腐植酸改性后增强了对水中铅镉的吸附能力。     

粉煤灰/膨润土颗粒的制备与pb2+吸附实验

以天然钙基膨润土和燃料废弃物粉煤灰为原料,工业淀粉为致孔剂,采用挤出-滚圆技术,制备了粉煤灰/膨润土复合颗粒吸附剂,并用于含Pb~(2+)溶液的吸附。研究了吸附时间、pH、投样量和溶液初始浓度对吸附性能的影响。结果表明,采用挤出-滚圆法制得的复合颗粒吸附剂大小均匀,表面没有裂纹,具有良好的机械强度。吸附实验中,在投样量10.0 g/L,溶液pH为6,吸附时间120 min,溶液初始浓度100 mg/L时,复合颗粒吸附剂对Pb~(2+)的去除率达到97.40%,吸附量为9.74mg/g。热力学实验表明吸附剂对Pb~(2+)的吸附更符合Langmuir吸附等温模型。     

热处理褐铁矿去除水中的Mn2+

本文利用褐铁矿中针铁矿经热脱水相变获得以纳米晶赤铁矿为主要物相的纳米-微米多级孔结构材料,并用于模拟净化富Mn~(2+)地下水。同时考察了热处理温度、初始pH值、初始Mn~(2+)浓度、吸附反应时间等对材料去除溶液中Mn~(2+)的影响。XRD、TEM、BET表征结果表明,300℃热处理产物中赤铁矿孔径最小为2.7 nm,比表面积最大达到107.4 m~2/g。吸附实验结果表明,在pH值5~10的范围内,p H值对煅烧褐铁矿颗粒对Mn~(2+)去除效果影响较小;材料在贫氧条件下对水中低浓度Mn~(2+)的最大吸附量为6.45 mg/g;吸附动力学符合准二级动力学模型;褐铁矿热处理形成的纳米晶赤铁矿对Mn~(2+)具有吸附和催化氧化作用,其中的杂质锰氧化物对Mn~(2+)的吸附和催化氧化具有增强作用。     

H~+对Cu~(2+)—Me~(2+)二元体系吸附的影响规律研究

土壤对重金属离子的吸附容量严格受H~+浓度的控制。本文通过试验探讨了H~+ 对Cu~(2+)——Pb~(2+),Cn~(2+)——Zu~(2+),Cu~(2+)——Hg~(2+)系统中Cu~(2+)吸附量的影响规律。当pHpH时,Cu~(2+)吸附量随pH值增大而减小。对于酸性土,pH=6.5(初始值)或7.0(平衡值),对碱性土,pH=5.5(初始值)或7.8(平衡值)。在pHpH_(ZPC)时,吸附模式具有完全不同的形式。     

面包酵母菌吸附黄铜矿微生物浸出矿液中Cu~(2+)的试验研究

选用面包酵母菌为吸附菌株,研究了菌株吸附黄铜矿微生物浸出矿液中Cu2+的吸附富集过程,探讨了吸附试验中pH值、温度和初始菌体加入量对Cu2+吸附效果的影响。结果表明:在酵母菌吸附Cu2+的过程中,菌体细胞上的蛋白质酰胺和多糖等成分更多地参与了吸附Cu2+的过程,Cu2+与菌体表面的有机基团结合形成颗粒物沉淀附着在细胞壁上。菌株动力学吸附分析中发现,实验用各菌株对Cu2+的动力学吸附过程除了受菌株种属的影响外,还应与菌株的细胞壁形貌、菌株本身的生长状况的等因素相关。在pH=4.5、t=30℃、初始菌体加入量8.0 g/L的条件下,吸附反应14 h后酵母菌的最佳铜吸附率可达66.64%,面包酵母菌可以吸附富集黄铜矿微生物浸出矿液中的Cu2+,可以有效回收低品位黄铜矿中的铜资源。     

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。     

凹凸棒石铁/铝氢氧化物纳米复合材料对磷的吸附动力学研究

用铁/铝盐水解法制备了凹凸棒石/铝氢氧化物(PNCMⅠ)、凹凸棒石/铁氢氧化物(PNCMⅡ)和凹凸棒石/铁铝氢氧化物(PNCMⅢ)3种凹凸棒石纳米复合材料。对比了这3种纳米复合材料对水中磷的吸附净化能力,并利用吸附动力学实验探讨了3种材料对磷的吸附机理。结果发现:负载了铝/铁氢氧化物后凹凸棒石的晶体结构没有改变;温度对于3种吸附剂吸附磷的动力学参数影响不显著;3种吸附剂对磷的实际吸附量、理论吸附量和初始吸附速率均随着磷的初始浓度增大而增大。PNCMⅠ对磷的理论吸附量为18.18 mg/g,较其他2种吸附剂大。当磷的初始浓度从5 mg/L增加到50 mg/L,PNCM I对磷的初始吸附速率从0.125 mg/(g·min)增加到1.425 mg/(g·min)。3种凹凸棒石黏土纳米复合材料对磷的吸附符合准二级动力学方程,表明其吸附均为化学吸附。     

膨润土尾矿复合陶粒制备与Cr(Ⅵ)吸附性能

膨润土提纯后的尾矿主要含石英、斜绿泥石和白云母等矿物,以尾矿为主原料制备了复合陶瓷颗粒,采用XRD,IR和SEM探讨了烧结工艺对结构变化的影响,研究了复合陶瓷颗粒的组分变化、烧结温度、pH、初始浓度、吸附时间和温度对Cr(Ⅵ)离子吸附效果的影响,探讨了动力学和热力学变化。结果表明,烧结温度对吸附影响不大,烧结适宜温度为1000℃,陶瓷颗粒的主晶相为石英和硅灰石,表面为不均匀多孔结构。吸附的最佳吸附条件是pH值1、陶瓷颗粒用量1 g、吸附时间12 h及铬离子初始浓度100 mg/L,吸附率达96.33%。吸附行为符合准二级动力学方程,属于单分子层化学吸附;热力学数据说明,吸附反应为自发吸热反应。     

Fractal kinetic characteristics for dissolving and leaching processes of strontium residue

The pore structural characteristics of strontium residue were studied with the N₂ adsorption method (ASAP2010). The kinetic properties concerning dissolving and leaching strontium waste were described by determining the concentrations of Sr²⁺, Ba²⁺ and soluble sulphides in solutions. The results showed that the specific surface area and pore volume increased with decreasing granule diameter, and the micropore surface of the residue was fractal. In the dissolving and leaching processes of strontium residue, soluble ion concentrations increased with decreasing granule diameter of the residue, and the reaction dimension was lower than the fractal dimension of pore surface. Sr²⁺ and soluble sulphide concentrations significantly exceeded the defined standard values, while Ba²⁺ concentrations did not, either in the dissolving or leaching solutions. In addition, dissolving and leaching reactions selectively occurred on the micropore surface of strontium residue.     

The impacts of common ions on the adsorption of heavy metal

Researches on the impact of common ions onto sediments are of great importance for the study of the heavy metal adsorption mechanisms. Considering the surface sediments from the relatively clean reach in the Baotou section of the Yellow River as the adsorbent, this work presents the impacts of common ions (Na⁺, Mg²⁺, K⁺, Ca²⁺, Cl⁻, SO₄ ²⁻, and NH₄ ⁺) on heavy metals (Cu²⁺, Zn²⁺, Cd²⁺, and Pb²⁺) adsorption. The experimental results reveal that the adsorptive capacities of the heavy metals are controlled by different adsorption mechanisms in different ion concentration ranges. With the increase of the ionic strength, the adsorption of the heavy metals increases for the compression of the electric double layer, whereas decreases for the decreasing of the ionic activities of the heavy metals. The competitive adsorption and complexations between the heavy metals and common ions are also important factors controlling the heavy metal adsorption. According to the experimental results and the real concentration of common ions in the Baotou section of the Yellow River, the increase of the concentrations of Na⁺, Mg²⁺, K⁺, and Ca²⁺ would cause the increase of Zn²⁺ adsorption and reduce the Zn pollution. The NH₄ ⁺ from the industrial discharge of the tributaries has a strong impact on the heavy metal adsorption.     

Biosorption characteristics of heavy metals (Ni2+, Zn2+, Cd2+, Pb2+) from aqueous solution by Hizikia fusiformis

Heavy metal ions (Pb²⁺, Cd²⁺, Ni²⁺, and Zn²⁺) were biosorbed by brown seaweed (Hizikia fusiformis), which was collected from Jeju Island of South Korea. The metal adsorption capacity of H. fusiformis improved significantly by washing with water or by base or acid treatments. The maximum sorption by NaOH-pretreated biomass was observed near a slightly acidic pH (pH 4?6) for Pb²⁺, Cd²⁺, Ni²⁺, and Zn²⁺. This result suggests that the treatment of H. fusiformis biomass with NaOH helped increase the functional forms of carboxylate ester units. Kinetic data showed that the biosorption occurred rapidly during the first 60 min, and most of the heavy metals were bound to the seaweed within 180 min. The maximum metal adsorption capacities assumed by a Langmuir model were on the order of Pb²⁺ > Cd²⁺ > Ni²⁺ > Zn²⁺. Equilibrium adsorption data for the heavy metal ions could fit well in the Langmuir model with regression coefficients R ² > 0.97.     

Adsorption kinetics and intraparticulate diffusivities of Hg, As and Pb ions on unmodified and thiolated coconut fiber

As, Hg and Pb are examples of heavy metals which are present in different types of industrial effluents responsible for environmental pollution. Their removal is traditionally made by chemical precipitation, ion-exchange and so on. However, this is expensive and not completely feasible to reduce their concentrations to the levels as low as required by the environmental legislation. Biosorption is a process in which solids of natural origin are employed for binding the heavy metal. It is a promising alternative method to treat industrial effluents, mainly because of its low cost and high metal binding capacity. The kinetics was studied for biosorption experiments using coconut fiber for As (III), Hg (II) and Pb (II) ions adsorption. The specific surface area and surface charge density of the coconut fiber are 1.186×10²⁵ (m²/g) and 5.39 ×10²⁴ (meq/m²), respectively. The maximum adsorption capacity was found to be the highest for Pb (II) followed by Hg (II) and As (III). The modification of the adsorbent by thiolation affected the adsorption capacity. Equilibrium sorption was reached for the metal ions at about 60 min. The equilibrium constant and free energy of the adsorption at 30 °C were calculated. The mechanism of sorption was found to obey the particle-diffusion model. The kinetic studies showed that the sorption rates could be described by both pseudo first-order and pseudo second-order models. The pseudo second-order model showed a better fit with a rate constant value of 1.16 × 10^?4/min. for all three metal ions. Therefore, the results of this study show that coconut fiber, both modified and unmodified, is an efficient adsorbent for the removal of toxic and valuable metals from industrial effluents.     

Strontium behavior in the aragonite-calcite transformation: An experimental study at 40–98°C

The behavior of strontium during the replacement of aragonite by calcite, in a closed system between 40°C and 98°C, has been experimentally investigated. The experiments were conducted in CaCl₂ solutions, with and without NaCl. The distribution coefficient of strontium in calcite (λ_Sr^2+C) was found to be affected only slightly by temperature changes, and almost insignificantly by the presence of NaCl. λ_Sr^2+C values at 0.01 m_Ca²⁺ (its concentration in normal sea water) are: 0.055 at 40°C and 0.058 at 98°C. These results indicate that the low (around 500 ppm) concentration of strontium in ancient limestones could have been brought about by aragonite-to-calcite transformation in a system open to sea water, and are not necessarily indicative of replacement in fresh waters.     

Heavy metal biosorption potential of a Malaysian Rhodophyte (<Emphasis Type="Italic">Eucheuma denticulatum</Emphasis>) from aqueous solutions

Biosorption is a promising technology for the removal of heavy metals from industrial wastes and effluents. In the present study, biosorption of Pb²⁺, Cu²⁺, Fe²⁺ and Zn²⁺ onto the dried biomass of Eucheuma denticulatum (Rhodophyte) was investigated as a function of solution pH, contact time, temperature and initial metal ion concentration. The experimental data were evaluated by Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherm models. The sorption isotherm data followed Langmuir and Freundlich models, and the maximum Langmuir monolayer biosorption capacity was found as 81.97, 66.23, 51.02 and 43.48 mg g^?1 for Pb²⁺, Cu²⁺, Fe²⁺ and Zn²⁺, respectively. The sorption kinetic data followed pseudo-second-order and intraparticle diffusion models. Thermodynamic study revealed feasible, spontaneous and endothermic nature of the sorption process. Fourier transform infrared analysis showed the presence of amine, aliphatic, carboxylate, carboxyl, sulfonate and ether groups in the cell wall matrix involved in metal biosorption process. A total of nine error functions were applied in order to evaluate the best-fitting models. We strongly suggest the analysis of error functions for evaluating the fitness of the isotherm and kinetic models. The present work shows that E. denticulatum can be a promising low-cost biosorbent for removal of the experimental heavy metals from aqueous solutions. Further study is warranted to evaluate its potential for the removal of heavy metals from the real environment.     

Surface complexation model for strontium sorption to amorphous silica and goethite

Strontium sorption to amorphous silica and goethite was measured as a function of pH and dissolved strontium and carbonate concentrations at 25°C. Strontium sorption gradually increases from 0 to 100% from pH 6 to 10 for both phases and requires multiple outer-sphere surface complexes to fit the data. All data are modeled using the triple layer model and the site-occupancy standard state; unless stated otherwise all strontium complexes are mononuclear. Strontium sorption to amorphous silica in the presence and absence of dissolved carbonate can be fit with tetradentate Sr²⁺ and SrOH⁺ complexes on the β-plane and a monodentate Sr²⁺complex on the diffuse plane to account for strontium sorption at low ionic strength. Strontium sorption to goethite in the absence of dissolved carbonate can be fit with monodentate and tetradentate SrOH⁺ complexes and a tetradentate binuclear Sr²⁺ species on the β-plane. The binuclear complex is needed to account for enhanced sorption at hgh strontium surface loadings. In the presence of dissolved carbonate additional monodentate Sr²⁺ and SrOH⁺ carbonate surface complexes on the β-plane are needed to fit strontium sorption to goethite. Modeling strontium sorption as outer-sphere complexes is consistent with quantitative analysis of extended X-ray absorption fine structure (EXAFS) on selected sorption samples that show a single first shell of oxygen atoms around strontium indicating hydrated surface complexes at the amorphous silica and goethite surfaces.     

Removal of lead(II) from aqueous stream by hydrophilic modified kapok fiber using the Fenton reaction

A hydrophilic kapok fiber was prepared by a chemical process of the Fenton reaction and used as an adsorbent to remove Pb(II) from aqueous solution. The effects of experimental parameters including pH, contact time, Pb(II) concentration, and coexisting heavy metals were estimated as well as evaluated. The optimum concentrations of FeSO₄ and H₂O₂ for the Fenton reaction-modified kapok fiber (FRKF) were 0.5 mol L^?1 and 1 mol L^?1, respectively. The adsorption kinetic models and isotherm equations of Langmuir and Freundlich were conducted to identify the most optimum adsorption rate and adsorption capacity of Pb(II) on FRKF. The FRKF displayed an excellent adsorption rate for Pb(II) in single metal solution with the maximum adsorption capacity of 94.41?±?7.56 mg g^?1 at pH 6.0. Moreover, the FRKE still maintained its adsorption advantage of Pb(II) in the mixed metal solution. The FRKF exhibited a considerable potential in removal of metal content in wastewater streams.     

Hydrologic Dynamics of a Subtropical Estuary Using Geochemical Tracers,Celestún,Yucatan, Mexico

Oxygen isotopes and strontium concentrations were used as geochemical tracers to discern the sources of water to Celestún Lagoon, a small subtropical estuary on the western side of the Yucatán Peninsula of Mexico. Celestún Lagoon is underlain by karstified limestone with numerous locations where groundwater is observed discharging directly to the lagoon. In this study, samples of groundwater, lagoon surface water, and seawater (SW) were collected in April 2008 and June 2009 and analyzed for salinity, stable isotopes of oxygen, and strontium (Sr²⁺) concentrations. These geochemical tracers were used in two tertiary mixing models to calculate the relative ratio inputs of fresh groundwater, brackish groundwater, and SW to the lagoon. Two sources of groundwater were found to contribute to the surface water in the lagoon; one fresh and the other brackish with an average salinity of 19 psu. The fresh groundwater had an oxygen isotopic signature (δ¹⁸O) and strontium concentration (Sr²⁺) of δ¹⁸O?=?-3.30‰ and Sr²⁺?=?0.03 mmol/l, respectively. The brackish groundwater observed in the northern end of the lagoon add a dissimilar oxygen isotopic signature and Sr²⁺ concentration of δ¹⁸O?=?3.01‰ and Sr²⁺?=?0.12 mmol/l, respectively. Local SW had an isotopic oxygen signature and Sr²⁺ concentration between the two fresher sources (δ¹⁸O?=?1.40‰, Sr²⁺?=?0.09 mmol/l). The lagoonwide results of the two tracer mixing models (δ¹⁸O and Sr²⁺) agreed well (within 5 %) and indicated a ratio of brackish groundwater–fresh groundwater– SW of 31 %–26 %–43 % (±5 %) for the Sr²⁺ model and 35 %–25 %–40 % (± 5 %) for the δ¹⁸O model. Brackish groundwater is dominant in the northern portion of the lagoon, while SW dominates the southern portion. Fresh groundwater discharge is a significant contributor of water along the entire eastern boundary of the lagoon where mangrove forests are the dominant vegetation.     

Strontium,SO42−/Cl− and Mg2+/Ca2+ ratios as tracers for the evolution of seawater into coastal aquifers: the example of Castell de Ferro aquifer (SE Spain)

The strontium content and the SO₄^2?/Cl^? and Mg²⁺/Ca²⁺ ratios were used as natural tracers of the residence time of seawater intrusion into the Castell de Ferro aquifer. Analysis of these parameters indicated the existence of two principal flowpaths in the aquifer. The first flows through the eastern part of the aquifer, through the karstified Castell de Ferro massif; it accommodates a larger and more rapid flow, so that the residence time is shorter, leading to lower SO₄²⁺/Cl^? ratios, lower Sr²⁺ content and higher Mg²⁺/Ca²⁺ ratios. The second flowpath is in the western sector, and flows exclusively through alluvial deposits; the flow here is slower, particularly that flowing towards the sea. Thus the residence time of the water here will be longer and there is scant flushing of the intruded seawater; this is manifested in the high Sr²⁺ content, high SO₄²⁺/Cl^? and low Mg²⁺/Ca²⁺ ratios. To cite this article: P. Pulido-Leboeuf et al., C. R. Geoscience 335 (2003).