齐齐哈尔碾子山麦饭石物化性能及其对Pb2+、Cd2+、Cr3+的吸附行为研究

以齐齐哈尔碾子山麦饭石为研究对象,通过比表面积及孔隙分析、阳离子交换容量(CEC)测试以及p H值缓冲能力测试等,对碾子山区麦饭石的结构和性能进行表征,并进一步研究麦饭石对Pb~(2+)、Cd~(2+)、Cr~(3+)的吸附行为。结果显示:碾子山区麦饭石具有海绵体大孔结构,阳离子交换容量(CEC)13~20 mmol/100 g。碾子山麦饭石对酸碱溶液都具有较好的调节能力,尤其对酸液的调节更高效。重金属吸附性能方面,对Pb~(2+)、Cd~(2+)、Cr~(3+)这3种离子吸附关系为:Pb~(2+)Cr~(3+)Cd~(2+)。     

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。     

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。     

溶液中Pb~(2+),Cd~(2+)和Cu~(2+)离子对羟基磷灰石吸附Zn~(2+)行为的影响

本文研究了在Pb~(2+),Cd~(2+)和Cu~(2+)等离子共存的条件下,羟基磷灰石对溶液中Zn~(2+)离子的吸附行为,讨论了Pb~(2+),Cd~(2+)和Cu~(2+)离子对Zn~(2+)吸附行为的影响;比较了羟基磷灰石对上述离子的吸附能力。实验结果表明:随着Cd~(2+)离子浓度增大,对Zn~(2+)的去除率逐渐增高,羟基磷灰石对Cd~(2+)和Zn~(2+)离子无吸附选择性。而随着Cu~(2+)离子浓度增大,对Zn~(2+)的去除率急剧下降,表现出明显的吸附选择性。另一方面,对Zn~(2+)的去除率几乎不随Pb~(2+)离子浓度的变化而改变,这是由于羟基磷灰石对这两种离子的吸附行为与机理不同。上…     

鱼腥藻对某些金属离子的吸附效应研究（Ⅰ）

初步探讨了鱼腥藻对Mn~(2+)、Co~(2+)、Ni~(2+)、Cu~(2+)、Cd~(2+)和Pb~(2+)的生物吸附特性;研究了金属离子浓度与溶液pH值对吸附行为的影响;展示了某些藻类在分离富集中的应用前景。     

铁盐改性高岭土吸附结晶紫的研究

研究了高岭土的改性方法及最佳改性土对染料结晶紫的吸附性能,选择焙烧温度200℃,硫酸铁含量为2%,焙烧时间2 h,探讨了振荡时间、吸附剂投加量等因素对吸附的影响。实验结果表明,在30℃下改性高岭土对结晶紫吸附平衡时间为60 min,对150 mg/L结晶紫饱和吸附容量为17.32 mg/g;改性高岭土对结晶紫的吸附等温线与Langmuir型拟合较好,吸附动力学模式符合伪二级动力学方程。     

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。     

锌氧化物改性沸石对腐植酸的吸附机理

将锌氧化物负载在沸石分子筛上制备锌氧化物改性沸石吸附材料。通过XRD、SEM、BET、Zeta电位仪和Raman光谱等分析表征手段研究锌氧化物在沸石中的分散状态和表面带电性。通过动力学和热力学研究,探讨该改性吸附材料对腐植酸的吸附机理;并在相同条件下,与商品活性炭进行腐植酸吸附对比试验。研究结果表明:(1)在21±1℃,锌氧化物改性沸石对腐植酸的最大饱和吸附量达到60 mg/g;(2)锌氧化物改性沸石对腐植酸的吸附符合准二级动力学方程和Freundlich等温吸附模型;(3)锌氧化物改性沸石对腐植酸的吸附性能远高于商品活性炭。     

ZH型重金属螯合纤维对水溶液中Sr2+的吸附行为

研究了ZH型重金属螯合纤维对水溶液中Sr~(2+)的吸附行为,考察了pH值、纤维加入量、Sr~(2+)初始浓度、作用时间等对吸附行为的影响,并采用SEM、EDS和FTIR等现代分析测试手段探讨了ZH型重金属螯合纤维对Sr~(2+)的吸附机制。结果表明,在pH值为7.0、纤维加入量为2.0 g/L、Sr~(2+)初始质量浓度为50 mg/L的条件下,纤维对Sr~(2+)的吸附在4 h左右基本达到平衡。实验条件下ZH型重金属螯合纤维对Sr~(2+)的最大吸附量可达26.22 mg/g。等温吸附拟合结果表明,ZH型重金属螯合纤维对Sr~(2+)的吸附可能是以单分子层为主的单分子层和多分子层吸附共同作用的结果。纤维对Sr~(2+)的动力学吸附过程符合准二级动力学模型。红外光谱分析表明Sr~(2+)与纤维上—NH_2和—COOH等基团进行配位络合从而吸附在纤维表面,—CH_2—和C=CH_2等基团参与此吸附过程。能谱分析表明Sr~(2+)与纤维上Na~+和Ca~(2+)还存在着离子交换作用。     

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。     

Competitive adsorption of metal ions onto goethite–humic acid-modified kaolinite clay

A binary mixture of humic acid and geothite was prepared and used to modify kaolinite to produce geothite–humic acid (GHA)-modified kaolinite adsorbent useful for the adsorption of Pb²⁺, Cd²⁺, Zn²⁺, Ni²⁺ and Cu²⁺ from Single and Quinary (5) metal ion systems. The cation exchange capacity (CEC) and specific surface area of GHA-modified kaolinite clay adsorbent were found to be 40 meq/100 g and 13 m²/g, respectively, with the CEC being five times that of raw kaolinite clay (7.81 meq/100 g). The Langmuir–Freundlich equilibrium isotherm model gave better fit to experimental data as compared with other isotherm models. In Quinary metal ion system, the presence of Zn²⁺ and Cu²⁺ appears to have an antagonistic effect on the adsorption of Pb²⁺, Cd²⁺ and Ni²⁺, while the presence of Pb²⁺, Cd²⁺ and Ni²⁺ shows a synergistic effect on the adsorption of Zn²⁺ and Cu²⁺. The GHA-modified kaolinite showed strong preference for the adsorption of Pb²⁺ in both metal ion systems. Brouers–Weron–Sotolongo (BWS) kinetic model gave better fit to kinetic data compared with other kinetic models used. Data from BWS kinetic model indicate that adsorption of metal ions onto GHA-modified adsorbent in both metal ion systems followed strictly, diffusion-controlled mechanism with adsorption reaction proceeding to 50 % equilibrium in <2 min in the Single metal ion system and <1 min in the Quinary metal ion system. Adsorption of metal ions onto GHA-modified kaolinite is fairly spontaneous and endothermic in nature in both metal ion systems although the rate of metal ion uptake and spontaneity of reaction are reduced in the Quinary metal ion system.     

红外光谱-显微共焦激光拉曼光谱研究天然红宝石和蓝宝石中含水矿物包裹体特征

天然红宝石和蓝宝石的包裹体中常见典型的含水矿物包裹体,这些含水矿物包裹体容易受外界环境升温而发生改变。微量含水矿物包裹体变化会对红宝石和蓝宝石的物理和化学性质产生明显影响,该性质为宝石热处理的鉴定提供了检测思路。本文采集了天然红宝石和蓝宝石样品,用显微镜放大观察包裹体特征,结合红外光谱与显微共焦激光拉曼光谱测试研究了含水矿物包裹体的特征。结果表明:天然红宝石和蓝宝石样品中含水矿物包裹体的外观轮廓清晰,晶形完整;红外光谱在2000～3700cm~(-1)附近显示出2105～2110cm~(-1)和1977～1985cm~(-1)硬水铝石和3619cm~(-1)和3696cm~(-1)高岭石等水(H_2O或—OH等)的特征吸收峰;拉曼光谱中可见角闪石、云母、磷灰石和长石等结晶度较好的典型含水矿物包裹体的特征拉曼位移。该系列特征揭示了红宝石和蓝宝石样品中含有水的特征,可作为红宝石和蓝宝石天然成因且未经过热处理的鉴定依据。     

基于红外光谱技术研究内蒙古乌奴格吐山斑岩铜钼矿蚀变和矿化特征

近年来,红外光谱技术在矿物学研究、地质勘探与找矿等方面发挥了重要作用。本文通过测量与分析内蒙古乌奴格吐山斑岩铜钼矿Z661钻孔岩心短波红外和热红外波段的光谱,快速厘定了该矿床的蚀变矿物类型及组合特征。结果表明:乌奴格吐山斑岩铜钼矿床蚀变矿物主要有石英、钾长石、绢云母、伊利石、高岭石和蒙脱石等。蚀变矿物组合在空间上呈现出明显的分带性,其中石英+伊利石+绢云母+钾长石与矿化关系最为密切,可作为找矿的标型矿物组合;结合钻孔Cu、Mo矿化分布特征,发现绢(白云母)2200nm处吸收峰位置的波长偏移与成矿中心距离有关,波长变小,更趋向于成矿中心;且伊利石结晶度(IC)越大,结晶度较高,矿化程度强。因而,该技术方法通过蚀变矿物波谱,能够快速圈定斑岩铜钼矿蚀变矿物组合,进而提高勘查效率。     

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.     

原子荧光光谱测定土壤和水系沉积物中硒的干扰来源及消除方法

原子荧光光谱法(AFS)具有灵敏度高、结构简单、容易操作等优点,但目前测定土壤和沉积物中的硒等元素的标准方法所采用的消解过程繁琐,易产生干扰。沸水浴可以把土壤和水系沉积物中硒提取完全,本文根据样品中元素丰度和仪器性能,将AFS测定Se的干扰分为Cu和Pb两大类,根据实验提出在水浴消解液加入浓盐酸(不宜加入硫脲-抗坏血酸),通过增加溶液酸度和Cl~-浓度,即保持样品中盐酸浓度高于23%,可抑制Cu~(2+)还原为Cu~0和Pb~(4+)生成PbH_4,有效降低了Cu的负干扰和Pb的正干扰,提高了AFS测定Se的精密度和准确度。本方法测定Se的检出限为0.008mg/kg,测试标准物质的相对标准偏差为0.5%～11%,相对误差为-16.3%～9.5%;比行业标准HJ 680—2013的检出限(0.01mg/kg)、精密度(0.79%～23.1%)和准确度等技术指标更佳。     

A comparison of organic wastes as bioadsorbents of heavy metal cations in aqueous solution and their capacity for desorption and regeneration

The adsorption capacity of seven organic wastes/by-products (slash pine, red gum and western cypress bark, composted green waste, prawn exoskeletons, spent brewery yeast and mill mud from a sugar mill) for transition metals were determined at two metal concentrations (10 and 100 mg L⁻¹) and three equilibrium pH values (4.0, 6.0 and 8.0) in batch adsorption experiments. All tested materials indicate a positive affinity to adsorb metal cations from aqueous solution and spent yeast was the least effective. Adsorption generally increased with increasing pH and the order of selectivity of metals was: Cr³⁺ > Cu²⁺ > Pb²⁺ > Zn²⁺ ≥ Cd²⁺. For pine bark, compost, spent yeast and prawn shell, quantities of previously adsorbed Pb and Cd desorbed in 0.01 M NaNO₃ electrolyte were negligible. However, 0.01 M HNO₃, and more particularly 0.10 and 0.50 M HNO₃ were effective at removing both adsorbed Pb and Cd. Using 0.10 M HNO₃ as the regenerating agent, pine bark and compost maintained their Pb and Cd adsorption capacity over eight successive adsorption/regeneration cycles. For mill mud and prawn shell, there was a pronounced decrease in adsorption capacity after only one regeneration cycle. A subsidiary experiment confirmed that acid pre-treatment of the latter two materials appreciably reduced their Pb and Cd adsorption capacity. This was ascribed to the metal adsorption capacity of prawn shell and mill mud being partially attributable to their significant CaCO₃ content and acid treatment induces dissolution of the CaCO₃. It was shown that in relation to both adsorption capacity and desorption/regeneration capability, composted green waste showed the greatest potential.     

Influence of operating conditions on the removal of Cu, Zn, Cd and Pb ions from wastewater by adsorption

Nile Rose Plant was used to study adsorption of several cations (Cu²+, Zn²+, Cd²+ and Pb²+) from wastewater within various experimental conditions. The dried leaves of Nile Rose Plant were used at different adsorbent/ metal ion ratios. The influence of pH, contact time, metal concentration, and adsorbent loading weight on the removal process was investigated. Batch adsorption studies were carried out at room temperature. The adsorption efficiencies were found to be pH dependent, increasing by increasing the pH in the range from 2.5 to 8.5 exept for Pb. The equilibrium time was attained within 60 to 90 min. and the maximum removal percentage was achieved at an adsorbent loading weight of 1.5 g/50 mL mixed ions solution. Isothermal studies showed that the data were best fitted to the Temkin isotherm model. The removal order was found to be Pb²⁺> Zn²⁺> Cu²⁺> Cd²⁺. The surface IR-characterization of Nile rose plant showed the presence of many functional groups capable of binding to the metal cations.     

应用高温甲烷吸附实验研究川东北地区五峰组页岩甲烷吸附能力

页岩甲烷吸附能力是决定页岩气井开采方案的重要参数,对评估页岩气藏潜力意义重大。干酪根类型、总有机碳含量、矿物组成、成熟度和孔径等是影响页岩吸附性能的因素,但针对高温高压下过剩吸附现象对页岩甲烷吸附能力影响的研究还需开展进一步的探索。为揭示四川盆地东北地区五峰组页岩甲烷吸附能力,本文通过场发射扫描电镜、低温氮气吸附和高压甲烷吸附实验,研究了高温高压下页岩的甲烷吸附能力,并分析了页岩孔隙结构等对页岩吸附能力的影响。结果表明:①五峰组页岩孔隙结构非均质性强,发育有机孔隙、粒(晶)间孔隙、粒(晶)内孔隙和粒(晶)间溶孔等多种孔隙;②比表面积平均为19.1282m^2/g;孔体积平均为0.0195cm^3/g;孔径平均为5.2226nm;③修正后的饱和吸附气量为2.56m^3/t;④五峰组页岩甲烷吸附性能受控于比表面积、孔体积;有机质含量越大、有机质热演化程度越低,其甲烷吸附性能越强;⑤孔隙结构是影响页岩甲烷吸附能力的重要内因。同时指出低压条件下的实验吸附曲线不适合直接评价页岩甲烷吸附能力。     

新型荧光碳点的制备及其在微量金属离子测定中的应用

碳点(CD)具有粒径小、抗光漂白性好、荧光稳定性高、发射光谱可调、表面易功能化、毒性低及生物相容性好等优点,已在催化、生物成像、药物传递、荧光检测、光电子器件等方面得到了广泛的应用。近年来,利用不同原料制备高性能荧光CD的合成方法备受关注。此外,通过CD直接与目标分析物相互作用,特异性配体修饰后的CD与目标分析物相互作用、CD与其他物质形成复合物后与目标分析物相互作用构建荧光探针,并将其用于微量金属离子的检测得到了迅速发展和广泛应用。本文阐述了CD的光学性质和合成原料,对其常用的自上而下法和自下而上法两类合成方法的过程及特点进行了总结。在此基础上,详细评述了基于CD与目标分析物的三种相互作用方式所构建的荧光探针在测定Fe^3+、Zn^2+、Cu^2+等具有生化作用的离子和Hg^2+、As^3+、Pb^2+、Cr^6+、Cd^2+等重金属离子的应用进展。本文指出,深入研究检测机理,发展新型检测模式,针对特定金属离子和样品组成设计构建荧光探针,建立可用于复杂样品的分析方法是开展构建新型CD荧光探针所面临的挑战和发展方向。