恶臭假单胞菌与土壤矿物的界面反应及其对甲基对硫磷降解影响

研究了恶臭假单胞菌在蒙脱石、高岭石和针铁矿表面的吸附特征,探讨了细菌在不同粘粒矿物存在下的生长代谢活性,及对甲基对硫磷的降解动力学.结果表明, 三种矿物对细菌的吸附强度为针铁矿>高岭石>蒙脱石.当甲基对硫磷浓度较低时(10 mg/L), 游离菌的降解能力始终比固定菌强;在高浓度(20～40 mg/L)下, 固定菌对农药的降解能力起初(前9 h)高于游离菌, 随后渐渐低于游离菌.不同矿物固定的细菌, 其降解能力为蒙脱石>高岭石>针铁矿.蒙脱石对细菌的亲和力最弱, 但它对细菌的代谢活性有促进作用, 有利于农药的生物降解; 而针铁矿与细菌的结合强度最大, 细菌活性受到抑制, 不利于农药的降解.     

"中性"粘土矿物对非水溶液中有机碱的吸附

理想品格中无同晶转换，因而不带层电行的中性粘土矿物（即：1：1型的高岭石，板状蛇纹石和2：1型的叶蜡石，滑石）对非极性有机溶剂中有机碱（偶氮苯化合物，pKa＝1.5-5.0）的吸附等温线均属于Langmuir型，且吸附在矿物表面的有机碱均由其碱型变为酸型.偶氮苯化合物的pKa越大，被吸附的量越多在溶剂为正己烷和二硫化碳时粘土的吸附能力比溶剂为苯时高.这些结果说明不带层电行的粘土矿物表面存在着酸位.蒙脱石的酸位数量明显地储存于阳离子种类，但在Na＋、Ca2＋、Mg2＋饱和的条件下高岭石的改位数量几乎相同.随着相对湿度的增加;两矿物对甲基黄的吸附量均减少，但减少的方式明显不同、因此1：1型高岭石和2：1型叶蜡石一样，也具有与蒙脱石不同的表面酸性起源。     

针铁矿对焦磷酸根的吸附特征及吸附机制

为深入了解自然水体中焦磷酸盐的迁移转化行为,以表生环境中广泛存在的稳定矿物-针铁矿为研究对象,系统研究了其对焦磷酸根的吸附过程,探索了不同实验条件下(pH值、电解质、时间、温度)针铁矿对焦磷酸根吸附的影响。 结果表明,溶液pH值从6.27升至10.99时,总磷吸附量从3.00 mg/g降低至0.75 mg/g;电解质浓度越低越有利于针铁矿对焦磷酸根的吸附;吸附剂对焦磷酸根的吸附量在最初1 h内增长较快,随后渐渐达到吸附平衡;溶液温度的升高对吸附量提高具有增强作用。 用动力学和热力学模型对吸附过程进行拟合,发现准二级动力学和Langmuir模型具有更好的适用性。 结合材料吸附焦磷酸根前后的表征,推导出针铁矿对焦磷酸根的吸附机制可能是以表面配合和物理吸附为主导。     

红壤可变电荷矿物的酸碱缓冲能力及表面络合模型

氧化铁和高岭石是红壤中可变电荷的主要来源,对红壤的酸碱变化起到缓冲作用.本研究基于红壤矿物的表征和酸碱滴定实验结果,采用1-site/2-pK表面络合模型获得了其表面活性位点浓度H_s、密度D_s、酸碱平衡常数pK_a^int以及电荷零点pH_pzc等相关参数,定量解析了氧化铁和高岭土的酸碱缓冲能力.结果表明：该模型能较好地适用于分析针铁矿、赤铁矿及高岭石的表面酸碱性质;针铁矿、高岭石表面活性位点浓度H_s较高,说明其对酸具有较好的缓冲效果.根据上述酸碱性质参数,模拟计算了不同pH下的矿物表面化学物种,揭示了矿物表面反应缓冲土壤酸碱变化的机制.采用上述酸碱滴定方法及模型计算方法,分析实际林地红壤样品的酸碱缓冲能力,并采用表面络合模型计算了其表面化学物种,验证了该方法用于林地红壤酸碱缓冲能力分析的可行性.     

N-(2-氨乙基)-月桂酰胺浮选铝硅酸盐矿物的研究

研究了N (2 氨乙基) 月桂酰胺对高岭石、伊利石和叶腊石等铝硅酸盐矿物的浮选行为.发现该表面活性剂对叶腊石的浮选回收率最高可达97.7％，对伊利石和高岭石的回收率相对较低，一般不超过82％.矿浆pH对高岭石、伊利石和叶腊石的回收率影响较小.酸性矿浆中表面活性剂通过静电引力吸附在矿粒表面；碱性矿浆中，表面活性剂通过氢键吸附在矿粒表面.红外吸收光谱证明，三种矿物表面中均存在－OH；在一个较宽的pH范围内，三种矿物矿浆的Zeta电位均为负值，表明矿粒表面荷负电.矿粒的扫描电镜（SEM）照片（×15000）表明，叶腊石主要呈薄片状颗粒，高岭石和伊利石颗粒呈不规则形状.     

铝掺杂针铁矿的制备、表征及吸附氟的特性

水热条件下制备了针铁矿(Goe)和几种铝掺杂针铁矿(Goe-Al_(0.1),Goe-Al_(0.2)和Goe-Al_(0.4)),用X射线衍射(XRD)、扫描电镜(SEM)、氮气物理性吸附、酸碱滴定等手段对样品进行了表征,并研究了它们对氟离子的吸附特性。结果表明,随着铝掺杂量的增加,铝掺杂针铁矿的结晶度不断减弱、颗粒的长度不断减小。4种样品的微孔表面积、孔体积和表面分形度都表现为GoeGoeAl0.1Goe-Al_(0.2)Goe-Al_(0.4),而孔径分布表现为相反的顺序。Goe、Goe-Al_(0.1)、Goe-Al_(0.2)和Goe-Al_(0.4)的电荷零点(PZC)分别为8.2、8.3、8.5和8.7,pH=5.0时它们的表面电荷量分别为0.66、0.83、1.03和1.19 mmol·g~(-1)。准二级动力学模型适合描述4种样品对氟的吸附动力学过程,表明化学吸附是主要作用机制。一位Langmuir模型可较好的拟合等温吸附数据(R2为0.967~0.981),二位Langmuir模型对等温吸附数据的拟合度更高(R2为0.982~0.995),而Freundlich模型的拟合度较低(R2为0.877~0.912)。初始pH=5.0时,Goe、Goe-Al_(0.1)、Goe-Al_(0.2)和Goe-Al_(0.4)对氟的最大吸附容量分别为8.83、10.24、11.72和12.86 mg·g~(-1)。可见,铝掺杂针铁矿对土-水环境中氟的吸附容量高于纯针铁矿。     

CH_4和CO_2在油页岩中矿物质结构内部吸附的分子模拟

利用Materials Studio2017模拟软件构建了蒙脱石、高岭石、方解石和生石膏四种矿物质分子模型。采用巨正则蒙特卡洛(GCMC)方法和分子动力学(MD)方法对四种模型的吸附量和吸附热进行了模拟计算。研究表明,相同温度和压力条件下四种矿物质对CH_4和CO_2分子吸附量大小为:蒙脱石高岭石生石膏方解石;CH_4和CO_2分子的单组分吸附量随压力的增大而增大,两种气体吸附均符合Langmuir吸附规律;四种矿物质对CH_4和CO_2分子的等量吸附热均小于42 k J/mol,即为物理吸附;随着温度的升高,CH_4和CO_2分子的吸附量和吸附热均减小,且CH_4和CO_2分子的等量吸附热和等温吸附量之间呈良好的正相关。     

3种树脂对水溶液中单宁吸附性能的比较研究

通过静态吸附实验,研究了大孔吸附树脂NG-8、胺基化大孔吸附树脂NG-9和胺基化超高交联大孔吸附树脂NDA-99对水溶液中单宁的吸附行为特性.结果表明,3种树脂对单宁的吸附均符合Langmuir等温吸附方程,树脂对单宁的吸附容量NG-9＞NG-8＞NDA-99;吸附过程符合准二级动力学方程,吸附速率常数NG-8＞NG-9＞NDA-99.树脂的孔结构与表面化学性质是影响树脂吸附性能的重要因素.     

捕收剂ADTB对一水硬铝石和铝硅矿物的捕收性能

研究了自制新型螯合捕收剂ADTB对一水硬铝石、高岭石和伊利石的浮选行为。单矿物浮选试验表明,该捕收剂对一水硬铝石、铝硅矿物的捕收能力差别较大,能有效分离一水硬铝石与铝硅矿物。通过动电位测试实验研究了捕收剂对矿物的吸附机理。结果表明:捕收剂在一水硬铝石表面可能是通过-COOH、-NHOH与Al-O形成双环螯合物的化学吸附,而在高岭石、伊利石表面主要是物理吸附。通过与捕收剂油酸进行比较,证明ADTB是一种较好的铝土矿正浮选捕收药剂。     

油页岩飞灰对重金属离子的吸附动力学及热力学

采用批式振荡吸附法研究了燃油页岩电厂循环流化床锅炉飞灰对重金属离子Pb²+、Cu²+、Zn²+、Cd²+的吸附动力学及吸附热力学特性,并提出了吸附机理。结果表明,油页岩飞灰对Pb²+、Cu²+、Zn²+、Cd²+的吸附平衡数据符合Langmuir和Freundlich吸附等温方程,但Freundlich方程能够更好地描述吸附等温线。在油页岩飞灰对重金属离子吸附的初始阶段,拉格朗日准一级动力学方程、准二级动力学方程、Elovich方程、粒子内扩散模型均能很好地反映吸附模式,而整个吸附过程则遵循二级反应动力学方程,其吸附过程是液膜扩散和粒子内扩散共同作用的结果。油页岩飞灰对Pb²+、Cu²+、Zn²+、Cd²+的吸附是吸热反应。     

Preferential adsorption of extracellular polymeric substances from bacteria on clay minerals and iron oxide

The adsorption of extracellular polymeric substances (EPS) from Bacillus subtilis on montmorillonite, kaolinite and goethite was investigated as a function of pH and ionic strength using batch studies coupled with Fourier transform infrared (FTIR) spectroscopy. The adsorption isotherms of EPS on minerals conformed to the Langmuir equation. The amount of EPS-C and -N adsorbed followed the sequence of montmorillonite>goethite>kaolinite. However, EPS-P adsorption was in the order of goethite>montmorillonite>kaolinite. A marked decrease in the mass fraction of EPS adsorption on minerals was observed with the increase of final pH from 3.1 to 8.3. Calcium ion was more efficient than sodium ion in promoting EPS adsorption on minerals. At various pH values and ionic strength, the mass fraction of EPS-N was higher than those of EPS-C and -P on montmorillonite and kaolinite, while the mass fraction of EPS-P was the highest on goethite. These results suggest that proteinaceous constituents were adsorbed preferentially on montmorillonite and kaolinite, and phosphorylated macromolecules were absorbed preferentially on goethite. Adsorption of EPS on clay minerals resulted in obvious shifts of infrared absorption bands of adsorbed water molecules, showing the importance of hydrogen bonding in EPS adsorption. The highest K values in equilibrium adsorption and FTIR are consistent with ligand exchange of EPS phosphate groups for goethite surface. The information obtained is of fundamental significance for understanding interfacial reactions between microorganisms and minerals.     

Modeling the adsorption of Cd(II) onto Muloorina illite and related clay minerals

The adsorption of Cd(II) onto goethite, kaolinite, and illite was measured as a function of pH (adsorption edges) and concentration (adsorption isotherms) at 25 degrees C. As the pH was increased, adsorption onto goethite occurred mainly in the pH range 5.5-8, whereas adsorption onto kaolinite occurred in two stages, separated by a plateau in the pH region 5.5 to 7. Adsorption onto illite increased steadily as the pH was increased, with far less Cd(II) adsorbing onto illite than onto goethite or kaolinite per m(2) of mineral surface area. Potentiometric titrations of suspensions of each mineral, with and without Cd(II) present, were also completed. Results from all three types of experiments were modeled using an extended constant- capacitance surface complexation model. The reactions [Formula: see text] [Formula: see text] and [Formula: see text] best described Cd(II) adsorption onto goethite, while [Formula: see text] and [Formula: see text] best described Cd(II) adsorption onto kaolinite. A combination of the first, second, and fourth of these reactions best fitted the data for Cd(II) adsorption onto illite. In each case the model fitted all experimental data well. The results suggest that adsorption onto the variable charge (SOH) sites on illite more closely resembles adsorption onto goethite than onto kaolinite.     

Adsorption of UO2 2+ on natural composite materials

The prediction of the adsorption behavior of natural composite materials was studied by a single mineral approach. The adsorption of U(VI) on single minerals such as goethite, hematite, kaolinite and quartz was fully modeled using the diffuse-layer model in various experimental conditions. A quasi-thermodynamic database of surface complexation constants for single minerals was established in a consistent manner. In a preliminary work, the adsorption of a synthetic mixture of goethite and kaolinite was simulated using the model established for a single mineral system. The competitive adsorption of U(VI) between goethite and kaolinite can be well explained by the model. The adsorption behavior of natural composite materials taken from the Koongarra uranium deposit (Australia) was predicted in a similar manner. In comparison with the synthetic mixture, the prediction was less successful in the acidic pH range. However, the model predicted well the adsorption behavior in the neutral to alkaline pH range. Furthermore, the model reasonably explained the role of iron oxide minerals in the adsorption of U(VI) on natural composite materials.     

Effects of low-molecular-weight organic ligands and phosphate on DNA adsorption by soil colloids and minerals

Adsorption of DNA on montmorillonite, kaolinite, goethite and soil clays from an Alfisol in the presence of citrate, tartrate and phosphate was studied. A marked decrease in DNA adsorption was observed on montmorillonite and kaolinite with increasing anion concentrations from 0 to 5 mM. However, the amount of DNA adsorbed by montmorillonite and kaolinite was enhanced when ligand concentration was higher than 5 mM. In the system of soil colloids and goethite, with the increase of anion concentrations, a steady decrease was found and the ability of ligands in depressing DNA adsorption followed the sequence: phosphate > citrate > tartrate. Compared to H2O2-treated clays (inorganic clays), a sharp decrease in DNA adsorption was observed on goethite and organo-mineral complexes (organic clays) with increasing ligand concentrations. The results suggest that the influence of anions on DNA adsorption varies with the type and concentration of anion as well as the surface properties of soil components. Introduction of DNA into the system before the addition of ligands had the greatest amount of DNA adsorption on soil colloids and goethite. Organic and inorganic ligands promoted DNA adsorption on montmorillonite and kaolinite when ligands were introduced into the system before the addition of DNA. The results obtained in this study have important implications for the understanding of the persistence and fate of DNA in soil environments especially rhizosphere soil where various organic and inorganic ligands are active.     

Modeling the adsorption of citric acid onto Muloorina illite and related clay minerals

The adsorption of citric acid onto goethite, kaolinite, and illite was measured as a function of pH (adsorption edges) and concentration (adsorption isotherms) at 25 degrees C. The greatest adsorption was onto goethite and the least onto illite. Adsorption onto goethite was at a maximum below pH 5 and decreased as the pH was increased to pH 9. For kaolinite, maximum adsorption occurred between pH 4.5 and pH 7, decreasing below and above this pH region, while for illite maximum adsorption occurred between about pH 5 and pH 7, decreasing at both lower and higher pH. ATR-FTIR spectra of citrate adsorbed to goethite at pH 4.6, pH 7.0, and pH 8.8 were compared with those of citrate solutions between pH 3.5 and pH 9.1. While the spectra of adsorbed citrate resembled those of the fully deprotonated solution species, there were significant differences. In particular the C[bond]O symmetric stretching band of the adsorbed species at pH 4.6 and 7.0 changed shape and was shifted to higher wave number. Further spectral analysis suggested that citrate adsorbed as an inner-sphere complex at pH 4.6 and pH 7.0 with coordination to the surface most probably via one or more carboxyl groups. At pH 8.8 the intensity of the adsorbed bands was much smaller but their shape was similar to those from the deprotonated citrate solution species, suggesting outer-sphere adsorption. Insufficient citric acid adsorbed onto illite or kaolinite to provide spectroscopic information about the mode of adsorption onto these minerals. Data from adsorption experiments, and from potentiometric titrations of suspensions of the minerals in the presence of citric acid, were fitted by extended constant-capacitance surface complexation models. On the goethite surface a monodentate inner-sphere complex dominated adsorption below pH 7.9, with a bidentate outer-sphere complex required at higher pH values. On kaolinite, citric acid adsorption was modeled with a bidentate outer-sphere complex at low pH and a monodentate outer-sphere complex at higher pH. There is evidence of dissolution of kaolinite in the presence of citric acid. For illite two bidentate outer-sphere complexes provided a good fit to all data.     

Effect of iron oxide coatings on zinc sorption mechanisms at the clay-mineral/water interface

Oxide surface coatings are ubiquitous in the environment, but their effect on the intrinsic metal uptake mechanism by the underlying mineral surface is poorly understood. In this study, the zinc (Zn) sorption complexes formed at the kaolinite, goethite, and goethite-coated kaolinite surfaces, were systematically studied as a function of pH, aging time, surface loading, and the extent of goethite coating, using extended X-ray absorption fine structure (EXAFS) spectroscopy. At pH 5.0, Zn partitioned to all sorbents by specific chemical binding to hydroxyl surface sites. At pH 7.0, the dominant sorption mechanism changed with reaction time. At the kaolinite surface, Zn was incorporated into a mixed metal Zn-Al layered double hydroxide (LDH). At the goethite surface, Zn initially formed a monodentate inner-sphere adsorption complex, with typical Zn-Fe distances of 3.18 A. However, with increasing reaction time, the major Zn sorption mechanism shifted to the formation of a zinc hydroxide surface precipitate, with characteristic Zn-Zn bond distances of 3.07 A. At the goethite-coated kaolinite surface, Zn initially bonded to FeOH groups of the goethite coating. With increasing aging time however, the inclusion of Zn into a mixed Zn-Al LDH took over as the dominant sorption mechanism. These results suggest that the formation of a precipitate phase at the kaolinite surface is thermodynamically favored over adsorption to the goethite coating. These findings show that the formation of Zn precipitates, similar in structure to brucite, at the pristine kaolinite, goethite, and goethite-coated kaolinite surfaces at near neutral pH and over extended reaction times is an important attenuation mechanism of metal contaminants in the environment.     

Spectrophotometric determination of some insecticides with 3-methyl-2-benzothiazolinone hydrazone hydrochloride

A simple, rapid and sensitive spectrophotometric method is described for determining carbaryl, propoxur, fenitrothion and methyl parathion, based on reaction of their hydrolysis or reduction products (as appropriate) with 3-methyl-2-benzothiazolinone hydrazone hydrochloride in the presence of an oxidant (Ce(4+) or Fe(3+)) to give coloured species.     

Adsorption of cadmium(II) onto goethite and kaolinite in the presence of benzene carboxylic acids

The effect of benzene carboxylic acids on the adsorption of Cd(II) (5×10⁻⁵ M) by goethite and kaolinite has been studied in 0.005 M NaNO₃ at 25°C. The concentrations of phthalic (benzene-1,2-dicarboxylic acid), hemimellitic (1,2,3), trimellitic (1,2,4), trimesic (1,3,5), pyromellitic (1,2,4,5) and mellitic (1,2,3,4,5,6) acids varied from 2.5×10⁻⁵ to 1×10⁻³ M. Mellitic acid complexes Cd(II) strongly above about pH 3, but the other acids only at higher pH, phthalic acid forming the weakest complexes. Phthalic, trimesic and mellitic acids adsorbed strongly to goethite at pH 3, but adsorption decreased at higher pH; however, mellitic acid was still about 50% adsorbed at pH 9, by which the other two were almost entirely in solution. At 10⁻³ M all the acids enhanced the adsorption of Cd(II) to goethite, the higher members of the series being the most effective. The higher members of the series suppressed Cd(II) adsorption onto kaolinite, but phthalic and trimesic acids caused slight enhancement. The effects of mellitic acid on Cd(II) adsorption depended strongly on its concentration. The maximum enhancement of Cd(II) adsorption onto goethite was at 10⁻⁴ M. The greatest suppression of Cd(II) adsorption onto kaolinite was at 10⁻³ M, and at 2.5×10⁻⁵ M mellitic acid enhanced Cd(II) adsorption onto kaolinite at intermediate pH. The results are interpreted in terms of complexation between metal and ligand (acid), metal and substrate, ligand and substrate, and the formation of ternary surface complexes in which the ligand acts as a bridge between the metal and the surface.