硼吸附对针铁矿表面性质的影响

分析了针铁矿吸附硼酸根离子后表面电化学性质的变化及其对体系pH值的影响,并测定了比表面积,讨论了硼吸附后增加针铁矿对H+吸附的可能机制.结果表明,针铁矿吸附硼后,其电荷零点(PZC)下降,且下降幅度随吸附硼量的提高而加大.随着针铁矿吸附硼量的提高,针铁矿的比表面积也明显增大,对H+的次级吸附容量和吸附能力相应增大.     

Characterization of iron oxides in Fe-rich concretions from an imperfectly-drained Greek soil: a study by selective-dissolution techniques and X-ray diffraction

Fe-rich concretions commonly occur in Greek soils with alternating drying and waterlogging periods. This study was conducted to characterize the iron oxides in Fe-rich concretions from the upper solum of an Alfisol with seasonal perched water table by the combination of selective dissolution and X-ray diffraction (XRD) techniques. The results showed that more than 75% of the total iron (Fet) was associated with the crystalline and the amorphous Fe oxides, indicating a strong accumulation of free iron oxides (Fed) in concretions. Amorphous iron compounds (Feo) was present at high concentrations and fluctuated with profile depth. The active Fe ratio (Feo/Fed) values that ranged from 0.35 to 0.41 reflected an association of poorly crystalline goethite with some ferrihydrite. The XRD data showed that the Fe-rich concretions consisted of quartz, feldspars, illite and gypsum. The mineralogy of iron oxides in concretions was determined by comparison of XRD patterns for dithionite-citrate-bicarbonate (DCB) treated (deferrated) and untreated (non-deferrated) samples. Poorly crystalline goethite as demonstrated by broad lines in the diffraction patterns and ferrihydrite were the iron oxides detected in the concretions. This mineral assemblage appears to be related to the pedoenvironmental conditions in which the concretions were formed and indicates that the mechanisms governing the formation of crystalline Fe oxides from ferrihydrite are retarded by the presence of crystallization inhibitors.     

针铁矿-高岭石二元体的微观结构与形成机制

制备了针铁矿-高岭石复合物,以其混合物为对照,分析了它们的微观结构与形成机制。结果表明,复合物中的针铁矿较好地包被在高岭石表面,而混合物中两固相之间的包被作用微弱。相对针铁矿和高岭石两单体而言,二元体中针铁矿和高岭石的主要晶面间距没有明显变化;复合物的孔体积增多、平均孔径减小,混合物的孔体积和平均孔径都接近两单体的平均值;两种二元体的表面分形度(D)增大,且D混合物>D复合物。红外光谱显示,二元体中≡Fe-OH的振动频率升高,而≡Al-OH、Al-O、Si-O和Fe-O的振动频率降低;高岭石与针铁矿胶结后,核磁共振波谱中29Si和27Al的化学位移均向正方向移动。根据波谱分析的结果推断,针铁矿与高岭石的胶结主要通过针铁矿表面≡FenOH2(n/2)+(n=1,2,3)与高岭石表面≡Si-OH、≡Al-OH02.5+等Lewis酸之间的阳离子交换、高岭石表面≡Si-O-和≡Al-OH0.5-与针铁矿表面铁羟基(≡Fe-OH)间的阴离子交换以及高岭石表面O与针铁矿表面Fe间的配位等作用而实现,其胶结力主要为氢键和静电引力。复合物中≡Fe-OH、≡Al-OH等主要基团的振动频率以及29Si、27Al的化学位移的漂移均大于混合物中的变化量,说明复合物中针铁矿与高岭石间的胶结强度大于混合物中两固相间的胶结作用。     

Hydrolysis of cellobiose by β-glucosidase in the presence of soil minerals - Interactions at solid-liquid interfaces and effects on enzyme activity levels

Extracellular enzymatic activities in soils are essential for the cycling of organic matter. These activities take place in multiphase environments where solid phases profoundly affect biocatalytic activities. Aspergillus niger is ubiquitous in soils; its β-glucosidase plays an important role in the degradation of cellulose, and therefore in the global carbon cycle and in the turnover of soil organic matter. However, the information on the interactions of this protein with soil minerals is very limited, and even less is known about their consequences for the hydrolysis of the natural substrate cellobiose. We therefore characterised the sorptive interactions of this enzyme with the soil minerals montmorillonite, kaolinite and goethite and quantified the resulting changes in the hydrolysis rate of cellobiose. Fractions of adsorbed protein, and the resulting catalytic activity loss, were lower for montmorillonite than for kaolinite and goethite at given experimental conditions; adsorption was 9.7 ± 7.3% for montmorillonite, 70.3 ± 3.1% for kaolinite and 71.4 ± 1.8% for goethite, respectively. Adsorption of the protein to the minerals caused a total decrease in the catalytic activity of 18.8 ± 3.4% for kaolinite and 17.9 ± 4.7% for goethite whereas it was not significant for montmorillonite. The average catalytic activity lost by the pool of adsorbed molecules was 26.8% for kaolinite and 25.0% for goethite. Both the amount of adsorbed protein and the resulting loss of catalytic activity were found to be independent of the specific surface areas yet were influenced by the electrical properties of the mineral surfaces. Under the experimental conditions, montmorillonite and kaolinite are negatively charged whereas goethite is positively charged. However, because of the adsorption of phosphate anions from the buffer, a charge reversal took place at the surface of goethite. This was confirmed by zeta (ζ)-potential measurements in phosphate buffer, revealing negative values for all the tested minerals. Indeed goethite interacted with the enzyme as a negatively charged surface: the amount of adsorbed protein and the resulting catalytic activity loss were very similar to those of kaolinite. Our results show that, even if an important fraction of β-glucosidase is adsorbed to the minerals, the catalytic activity is largely retained. We suggest that this strong activity retention in presence of soil minerals results from a selective pressure on A. niger, which benefits from the activity of the adsorbed, and thus stabilized, enzyme pool.     

Sb(V)在三种矿物表面的吸附行为

用研究了蒙脱土、高岭土和针铁矿在不同的pH与离子强度的介质条件下对Sb(V)的吸附及解吸行为。3种矿物对Sb(V)的吸附能力差别较大,蒙脱土的吸附量远大于针铁矿和高岭土,针铁矿与高岭土的吸附能力相近。pH对Sb(V)在3种矿物表面的吸附行为影响显著。随pH的升高,Sb(V)的吸附均减弱。吸附在高岭土表面的Sb(V)易解吸,而针铁矿和蒙脱土表面的Sb(V)不易解吸。随离子强度升高,高岭土对Sb(V)的吸附减弱;离子强度对Sb(V)在针铁矿和蒙脱土表面吸附的影响较小。     

锰掺杂对针铁矿的结构、表面性质及吸附硒的影响

水热条件下制备了针铁矿(Goe)和不同含量锰掺杂产物(G-Mn0.1、G-Mn0.2、G-Mn0.3和G-Mn0.5),用X-射线衍射(XRD)、透射电镜(TEM)、氮气物理性吸附、Zeta电位分析、酸碱滴定等手段对样品进行了表征,并研究其对亚硒酸盐(Se(Ⅳ))和硒酸盐(Se(Ⅵ))的吸附特性。结果表明:低比例的锰掺杂(锰/铁的摩尔比RMn/Fe=0.1~0.2)显著促进了针铁矿晶体沿b轴方向生长,导致针铁矿颗粒的长径比增大,形貌由短纺锤体形变为大长径比的扁平针状;当RMn/Fe=0.3~0.5时,样品中出现了大量的掺锰磁铁矿,且针铁矿晶体的b轴方向生长受到严重的抑制而a轴方向生长受到一定程度的促进并导致针铁矿颗粒呈纤细状。Goe、G-Mn0.2和G-Mn0.5的比表面积分别为36.78、53.22和71.33 m2·g–1,表面分形度分别为2.31、2.53和2.59,平均孔径分别为13.73、15.59、6.92 nm,Zeta电位零点分别为7.36、6.58和5.31,pH5.0时的Zeta电位分别为40.5、35.3和4.92 mV。3种样品的表面活性羟基密度表现为Goe相似文献   

不同pH条件下针铁矿表面磷的配位形式及转化特点

应用ＸＰＳ技术研究了不同ｐＨ条件下针铁矿表面磷的配位形式及转化特点。结果表明：磷浓度－定时，低ｐＨ值有利于形成克的单基配位，高ｐＨ值有利于形成磷的双基配位。体系ｐ值升高，针铁矿表面的单基配位磷即较快地向双基配位磷转化；ｐＨ降低，双基配位磷则缓慢地向单基配位磷转化。分析认为，体系ｐＨ通过影响溶液中磷酸根的离子类型来影响针铁矿表面吸附磷的配位形式，ｐＨ变化引起表面磷酸根系子的解离和缔合，是导致针铁矿表     

Adsorption of Copper,Zinc, and Cadmium on Goethite,Aluminum‐Substituted Goethite,and a System of Kaolinite–Goethite: Surface Complexation Modeling

Abstract

Goethite, aluminum‐(Al)‐substituted goethite (GA2), and a system of kaolinite–goethite were examined for their ability to adsorb copper (Cu), zinc (Zn), and cadmium (Cd) as a function of pH, in two ionic strengths and two different metal concentrations. Specific surface area was determined by BET‐N₂, whereas the charge development on the solid surface was studied in the pH range ～3.5 to ～10.0 by potentiometric titration under continuous flow of argon.

Constant capacitance (CCM) and the double‐layer model (DLM) were used to fit the titration and adsorption data with the help of the least‐square optimization program FITEQL32. In both models, surface site density was fixed at Ns=2.31 sites nm^?2, whereas for CCM capacitance density was set at C=1.06. Alternatively, bibliographic suggestions for these two parameters were examined.

Aluminum‐substituted goethite exhibited higher specific surface area and adsorbed all three metals in lower pH values than the other solids. Moreover, GA2 exhibited point of zero salt effect (PZSE) higher than goethite, approaching that corresponding to Al₂O₃, possibly due to Al‐substitution, and the system exhibited PZSE values much higher than kaolinite, approaching that corresponding to goethite. The adsorption order for all three solids was Cu>Zn>Cd in any case, thus more Cu is adsorbed at a certain pH than Zn and even more than Cd, whereas the increase of metal concentration shifts the adsorption curve toward higher pH values.

Constant capacitance described the titration data satisfactorily, but by altering the Ns and C values, the fit became worse. Adsorption data are described by CCM, by emphasizing the formation of monodentate surface complex. Bidentate complex, in most of the cases, was of no importance in describing the data despite the evidence of its presence in recent spectroscopic studies for Cu and Cd on goethite. Alteration of Ns and C values worsened the fit in any case, and bidentate complex vanished. The DLM exhibited the worse fit in any case.     

鄂湘两省几种土壤中磷的有效性与氧化铁的类型

 鄂湘两省黄棕壤、红壤和棕红壤对磷的吸附特性、高粱幼苗的供磷效果及其与土壤物质组成关系的研究。结果表明：黄棕壤、红壤的磷吸附量和对磷的亲合力均明显高于棕红壤，它们吸附磷的解吸率和对高粱幼苗的供磷能力明显低于棕红壤。黄棕壤和红壤中的氧化铁为针铁矿型，棕红壤中的为针-赤混合型。供试土壤中针铁矿虽与赤铁矿形貌相似，呈片状，但由于其能吸附磷的比表面积比赤铁矿的大，故此氧化铁类型差异是导致黄棕壤、红壤与棕红壤中磷有效性显著不同的主要原因。     

针铁矿对重金属离子的竞争吸附研究

本文研究结果表明，Ｚｎ存在对Ｃｕ吸附影响很小，而Ｃｕ则明显干扰了Ｚｎ吸附，在金属浓度较高时，其干扰程度更显著。Ｎｉ和Ｃｏ并存使各自吸附量都有相应减少。表面络合常数用于表征表面对不同金属离子的相对选择性。Ｃｕ和Ｚｎ并存基本没有改变ｐＫＣｕ（ｉｎｔ），但使ｐＫＺｎ（ｉｎｔ）增大了２．１３单位；Ｎｉ和Ｃｏ并存使各自ｐＫＭ（ｉｎｔ）都有增大，在金属浓度较高时，Ｃｏ的ｐＫＭ（ｉｎｔ）增加值相对较大。这些结果