Adsorption of Cadmium and Zinc onto Micaceous Minerals: Effect of Siderophore Desferrioxamine B

The mobility, bioavailability, and environmental fate of heavy metals in soil are controlled by their adsorption onto soil minerals and solid organic matter. The adsorption is strongly affected by the presence of various low-molecular-weight organic acids. In this study, effect of hydroxamate siderophore desferrioxamine B (DFOB) on cadmium (Cd) and zinc (Zn) adsorption onto two micaceous clay minerals, muscovite and phlogopite, was evaluated in batch experiments. Results showed that the presence of DFOB diminished the adsorption of Cd and Zn onto both minerals, particularly under neutral to alkaline pH conditions. For instance, at pH 8.2, the presence of DFOB caused a decrease in the adsorption of Zn onto phlogopite by nearly 50%. The equilibrium adsorption of Cd and Zn was satisfactorily described using Freundlich isotherm. The adsorption isotherms showed that the affinity of Cd and Zn onto the minerals decreased in the presence of DFOB. For example, at pH 8.0, the presence of siderophore caused a decrease in the Freundlich adsorption isotherm coefficient K_F for Zn adsorption onto muscovite and phlogopite from 4.60 to 0.07 L g^-1 and from 3.56 to 0.36 L g^-1, respectively. These findings confirm the potential influence of siderophore on the fate of Cd and Zn in arid soils containing substantial contributions of micaceous silicate minerals.     

土壤矿物对有机质的吸附与固定机制研究进展

鉴于土壤有机质在生态系统及碳储存方面的重要性,关于土壤矿物对土壤有机质的吸附与固定机理方面的研究越来越受到了学术界的广泛关注。本文综述了近年来报道较多的土壤矿物对土壤有机质的吸附机制,以及主要影响因素。在众多矿物类型中,水合铁、铝氧化物及黏土矿物对有机质的吸附性较强,配体交换、络合、氢键、阳离子桥接、缩合及范德华力作用是土壤矿物与有机质之间的主要作用机制。土壤pH是影响矿物表面电荷及吸附位点的关键因素,进而影响矿物对有机质的吸附。土壤矿物表面的有机质含量对其继续吸附有机质具有一定的影响。吸附态有机质大多呈层状结构,越接近矿物表面的有机质与土壤矿物的结合越紧密。土壤有机质的稳定性受有机质与矿物间的作用力影响,一般而言,以化学键合吸附在矿物表面的有机质最稳定,其次为直接与矿物表面作用的电子"供体-受体"机制,范德华力和静电作用稳定性较差。近年来,随着分析设备和技术的进步,一些新的表征与探测方法(如热重分析、差示扫描量热法、傅里叶转换红外光谱、扫描电子显微镜、原子力显微镜、扫描透射X射线显微镜、中子散射技术等)被用于"矿物-有机质"结合机制的研究中,这些新手段毫无疑问会帮助更好地认识矿物与有机质间的作用机理。关于微生物在矿物吸附有机质、"矿物-有机质"复合体形成和演化过程中所起的作用,研究相对较少,但很明显这是至关重要的。     

土壤矿物质吸附砷的研究进展

砷是一种有毒的重金属元素,由于自然和人为的原因,世界上的许多国家存在砷污染问题,因此有关砷污染的研究与控制日益受到人们的关注。本文介绍了土壤砷污染的产生原因及污染状况,重点集中在探讨土壤中的各种矿物质对砷吸附行为的作用机理。这些矿物质包括铁铝氧化物和氢氧化物、锰氧化物、黏土矿物和碳酸盐类。关于砷在各类矿物质上的吸附机理,普遍接受的观点认为:砷氧阴离子与矿物质的表面发生了配位体交换过程并通过共价键的作用,形成了表面配位体。表面配位体以内层双齿双核鳌合形式为主,受矿物质的种类、pH值和氧化还原电位等因素的影响,外层吸附和其他鳌合状态可能存在。砷在土壤矿物质上的吸附效果强烈依赖于体系的pH值,这与吸附的理论模型和数学计算结果相一致。矿物质的种类、组成、结晶状态和表面积等影响了砷的吸附过程和吸附效果。土壤中存在的各种阴阳离子通过与砷阴离子竞争吸附位而影响砷在矿物质上的吸附。     

纳米粘土矿物对阿特拉津的吸附-解吸特性研究

采用批量平衡实验,研究了纳米粘土矿物与原粘土矿物对除草剂阿特拉津的吸附解吸特陛。结果表明,粘土矿物对阿特拉津的吸附-解吸均能用Freundlich方程很好地拟合。随着溶液中阿特拉津浓度的增加,粘土矿物对阿特拉津的吸附量增加;粘土矿物粒径越小,吸附量越大,纳米粘土矿物的吸附量显著大于原粘土矿物。粘土矿物对阿特拉津吸附量大小顺序为：纳米SiO2）纳米蒙脱石〉凹凸棒石〉蒙脱石〉SiO2。粘土矿物对阿特拉津的解吸表现出一定的滞后效应,即粘土矿物吸附的阿特拉津越多,解吸的越少。粘土矿物对阿特拉津的解吸率大小顺序为：SiO2〉凹凸棒石〉纳米蒙脱石〉纳米SiO2〉蒙脱石。     

几种土壤及黏土矿物对多氯联苯吸附特性的研究

采用批量平衡试验,研究了不同土壤及长黏土矿物对多氯联苯吸附特性。结果表明:多氯联苯浓度范围为0.25~5.0mg L-1时,不同土壤及黏土矿物对多氯联苯的吸附均能用Freundlich方程很好地拟合,随着溶液中多氯联苯浓度的增加,土壤及黏土矿物对多氯联苯的吸附量增加;几种土壤对多氯联苯吸附量大小顺序为:红壤>黄褐土>砂姜黑土,土壤有机质、粘粒等对多氯联苯吸附起主要作用,土壤更易吸附高氯代PCB77;黏土矿物对多氯联苯吸附量大小顺序为:纳米蒙脱石>纳米SiO2>凹凸棒石,黏土矿物吸附多氯联苯能力的大小与黏土矿物的比表面积、粒径、层状结构等有关;多氯联苯本身分子的大小影响其在黏土矿物上的吸附;土壤中添加黏土矿物可以提高对多氯联苯的吸附。     

Determination of Phosphate in Selective Extractions for Soil Iron Oxides by the Molybdenum Blue Method in an Automated Continuance Flow Injection System

Phosphorus (P) mobility and bioavailability in soil depend on the pools in which it resides. The identification of such pools is essential for the full understanding of P behavior in soil. We evaluated the molybdenum-blue ascorbic-acid method in an automated continuous flow injection analyzer (MB-FIA) to analyze P in two selective soil extractions for soil iron oxide (i.e., the acid ammonium oxalate, AAO, and citrate–dithionite, CD, procedures). Uninterrupted development of the color reaction was obtained at citrate and oxalate concentrations less than 50 mM and 35 mM, corresponding to molybdate/citrate and molybdate/oxalate molar ratios of 2.4 and 3.4, respectively. High precision (% RSD, 1.7 ± 1.3% for CD and 2.9 ± 3.7% for AAO), accuracy, and recoveries (105.7 ± 1.0% for CD and 99.8 ± 3.8% for AAO) were obtained. This study demonstrates the utility of the MB-FIA system for the determination of AAO- and CD-extractable inorganic P.     

平原区水田改林地后土壤黏土矿物及氧化铁的变化

近年来水田改为林地在我国南方地区非常普遍,为了解这种转变对土壤矿物(黏土矿物和氧化铁)演变的影响,在浙江省平原地区构建了4个水田改林地系列土壤,采用野外调查和室内分析相结合的方法,研究水田改林地后土壤剖面中氧化铁形态和黏土矿物类型的演变规律。结果表明,改林地后,土壤剖面中全铁含量变化不明显,耕作层和犁底层土壤游离氧化铁有轻微增加趋势。改林地15～20 a后,4个系列土壤耕作层活性铁和活化度降幅分别在18.0%～38.4%和24.7%～48.9%;耕作层土壤铁氧化物的晶胶比增幅在0.73倍～1.62倍;耕作层土壤亚铁含量明显下降,降幅最高达95.8%,变异系数达到143.9%;耕作层络合铁降幅在21.3%～36.2%,并与有机质呈极显著正相关(P<0.01)。改林地后,犁底层土壤中绿泥石相对含量及其与高岭石的比值都呈降低趋势,其他黏土矿物相对含量变化规律不明显,土壤有机质显著下降,土壤明显酸化。土壤铁氧化物形态和数量的变化对土壤结构以及土壤重金属的迁移转化等产生重要影响。     

有机修饰塿土对苯胺的吸附

以十六烷基三甲基溴化铵(CTMAB)单一修饰和CTMAB+十二烷基磺酸钠(SDS)混合修饰塿土耕层和粘化层土样,从吸附实验和热力学角度研究修饰土样对苯胺的吸附特征和机理。结果表明,供试土样对苯胺吸附均呈现100CB>50CB>120CS>CK的高低顺序,耕层修饰后对苯胺的平衡吸附量增大了4.5￣8.57倍,粘化层土样增大了6.0￣18.33倍;温度为40℃时耕层未修饰土样对苯胺的吸附量高于粘化层未修饰土样,20℃时则低于粘化层原土土样,而修饰土样则均呈现粘化层修饰土样对苯胺的吸附高于塿土耕层修饰土样的结果;耕层土样随温度升高苯胺平衡吸附量升高,而粘化层土样则表现出降温有利于苯胺吸附的现象,修饰剂对土样的修饰对苯胺的吸附具有"感温钝化"效应;Henry模型适用于描述苯胺的吸附;修饰土样对苯胺的吸附自由能变均为ΔG<0,属于自发反应,粘化层各土样对苯胺吸附为放热熵减过程,吸附自发性由焓减控制,耕层各土样对苯胺吸附为吸热熵增过程,其吸附自发过程为熵增控制过程;疏水吸附是修饰土样对苯胺吸附的主要机理,但修饰剂对于土壤表面的修饰是不均匀修饰,粘化层土样以物理吸附机制为主,耕层土样则存在化学吸附的机制。     

Composition of Typical Soil Minerals and Quantitative Analysis for Influence of Iron and Manganese Forms on Purple Soil Color in Northeastern Sichuan,China

Eurasian Soil Science - Eight soil samples from the Jurassic Shaximiao Formation (J2s) in the Sichuan Basin, China, were taken as the research object to explore the correlation and quantitative...     

Effects of Addition Sequence and pH of Oxalate on the Adsorption and Activity of Acid Phosphatase on Soil Colloids and Minerals

The adsorption and specific activities of acid phosphatase on soil colloids and minerals in oxalate systems with different pH values were studied using the batch method. Results indicated that the amount of phosphatase adsorption decreased in the following order: goethite ? yellow-brown soil (YBS) > kaolinite > latosol, and the specific activities of immobilized phosphatase were goethite > latosol > kaolinite > YBS. The profiles of enzymatic adsorption and specific activity on soil minerals were bell shaped, and their change tendencies were out of sync. The optimal pH for phosphatase adsorption was located between the isoelectric point of phosphatase and the zero point of charge of the studied soil minerals, and the optimal pH for the specific activity of the immobilized enzyme either did not change or shifted toward alkalinity. Enzymatic adsorption amounts and specific activities were greater when the enzyme was added before oxalate than when enzyme was added after oxalate.     

Adsorption behavior of the catechins and caffeine onto polyvinylpolypyrrolidone

Adsorbent is one of the most important factors for separation efficiency in fixed-bed purification techniques. The adsorption behavior of catechins and caffeine onto polyvinylpolypyrrolidone (PVPP) was investigated by static adsorption tests. The results showed that catechins rather than caffeine were preferred to adsorb onto PVPP since the adsorption selectivity coefficient of total catechins vs caffeine was around 22.5, and that adsorption of catechins could be described by the pseudo-second-order model. Adsorption amount of caffeine onto PVPP in green tea extracts solution was much higher than that in purified caffeine solution although the initial concentration of caffeine was similar in the two solutions, indicating the caffeine might be attached with catechins which were adsorbed by PVPP instead of being adsorbed by PVPP directly. The results also showed that the adsorption capacity of catechins and caffeine decreased with an increase in temperature, and that Freundlich and Langmuir models were both suitable for describing the isothermal adsorption of catechins, but not suitable for caffeine. The predicted maximum monolayer adsorption capacity of total catechins by PVPP was 671.77 mg g(-1) at 20 °C, which was significantly higher than that by other reported adsorbents. The thermodynamics analyses indicated that the adsorption of catechins onto PVPP was a spontaneous and exothermic physisorption process, revealing lower temperature was favorable for the adsorption of catechins. Elution tests showed that the desorption rates of catechins and caffeine were higher than 91% and 99% after two elution stages; in detail, almost all of the caffeine could be washed down at the water eluting stage, while catechins could be recovered at the dimethyl sulfoxide/ethanol solution eluting stage. Thus, the PVPP could be used as an excellent alternative adsorbent candidate for separating catechins from crude tea extracts, although some investigations, such as exploring the new eluants with low boiling point and high desorption efficiency, should be conducted furthermore.     

几种吸附剂对阿特拉津的吸附及其 Zeta 电位特性研究

通过振荡吸附平衡试验,研究了蒙脱石、凹凸棒石、竹炭、木炭对阿特拉津的吸附行为,讨论了pH值、离子强度对吸附的影响,并考察了吸附剂表面的Zeta电位变化。结果表明,几种吸附剂对阿特拉津的吸附均符合Freundlich方程;竹炭、木炭的吸附能力明显高于蒙脱石和凹凸棒石。吸附剂对阿特拉津的吸附量随着悬液离子强度的增加而增加,在悬液pH一定(pH=6),离子强度为10-3mol/L NaNO3时,蒙脱石、凹凸棒石对阿特拉津的吸附量分别为538.30、609.68 mg/kg,当离子强度增加为10-2mol/L时,吸附量分别增至611.26、731.63 mg/kg;当离子强度由10-3增至10-1mol/L NaNO3时,竹炭、木炭对阿特拉津的吸附量有较多增加。当悬液pH在3~8范围时,几种吸附剂表面均带负电荷,其Zeta电位值随着pH的增加而增加,随离子强度的增加而减小。悬液离子强度一定时,随着pH的增加,吸附阿特拉津后吸附剂表面Zeta电位变化不显著。研究结果有助于从机理上解析吸附剂对有机污染物的吸附行为。     

磷酸盐在水铁矿及水铁矿-胡敏酸复合体表面的吸附

The adsorption of phosphate onto ferrihydrite (FH) and two FH-humic acid (HA) complexes, obtained by co-precipitating FH with low (FH-HA1) and relatively high amounts of humic acid (FH-HA2), was studied through kinetics and isotherm experiments to determine the differences in phosphate adsorption between FH-HA complexes and FH and to reveal the mechanism of phosphate adsorption onto two soil compositions. The isoelectric point (IEP) and the specific surface area (SSA) of the mineral decreased as the particle porosity of the mineral increased, which corresponded to an increase in the amount of organic carbon. The adsorption capacity of phosphate was higher on FH than on FH-HA1 and FH-HA2 at the scale of micromoles per kilogram. The initial adsorption rate and adsorption affinity of phosphate decreased with an increase in the amount of HA in the mineral. The sensitivity of phosphate adsorption to the change in the pH was greater for FH than for FH-HA complexes. Ionic strength did not affect the adsorption of phosphate onto FH and FH-HA1 at a lower pH, and the increase in the ionic strength promoted phosphate adsorption at a higher pH. However, for the FH-HA2 complex, the increase in the ionic strength inhibited the adsorption of phosphate onto FH-HA2 at a lower pH and increased the adsorption at a higher pH.     

Adsorption of Acrylonitrile on Some Soils and Minerals from Aqueous Solutions

Equilibrium and kinetic studies have been made on the adsorption of acrylonitrile(CH2=CHCN) on three soils and four minerals from aqueous solutions.It was shown that the organic matter was the major factor affecting the adsorption process in the soils.The conformity of the equilibrium data to linear type(one soil) and Langmuir type(two soils) isotherms indicated that different mechanisms were involved in the adsorption.This behavior appears bo be related to the hydrophobicity of soil organic matter due to their composition and E4/E6 ratio of humic acids.The adsorption kinetics were also different among the soils,indicating the difference in porosity of organic matter among the soils,and the kinetics strongly affected the adsorption capacity of soils for acrylonitrile.Acrylonitrile was slightly adsorbed from aqueous solutions on pyrophyllite with electrically neutral and hydrophobic nature,and practically not on montmorillonite and kaolinite saturated with Ca.However,much higher adsorption occurred on the zeolitized coal ash,probably caused by high organic carbon content(107g/kg).     

褐煤基材料对Cd~(2+)的吸附机制

为筛选稳定、高效、环境友好的重金属污染修复材料,利用批吸附试验研究了不同温度下褐煤、腐植酸、活性炭对镉(Cd~(2+))的吸附特征,采用非线性χ~2检验辅助决定系数判断等温线模型拟合度,用红外光谱对材料功能团进行了识别。结果表明,Temkin模型能最好拟合3种材料对Cd~(2+)的等温吸附过程,Langmuir和Freundlich模型也能较好拟合但与温度有关。吸附热力学参数表明,3种材料对Cd~(2+)的吸附为优惠发生的物理吸附,并且是自发的吸热过程,3种材料与Cd~(2+)之间均有较强的作用力。在温度294.55~313.15 K时腐植酸、褐煤和活性炭对Cd~(2+)的最大吸附量分别为36.14~44.09、29.63~38.20 mg·g~(-1)和21.04~30.34 mg·g~(-1),吸附量随温度升高而升高,吸附自由能随着温度升高而降低,说明升温吸附更容易发生。准二级动力学拟合数据最好,表明3种材料对Cd~(2+)的吸附存在着化学过程。褐煤基活性炭和褐煤基腐植酸具有丰富的孔隙结构。红外光谱图表明腐植酸和褐煤较大的吸附量与其含氧功能团种类较多以及在波数2 360 cm~(-1)和2 342 cm~(-1)附近吸收峰有关。因此,褐煤基3种材料对Cd~(2+)的吸附是自发的吸热过程,腐植酸对Cd~(2+)的最大吸附量和吸附能力最大,用Temkin等温方程和准二级动力学曲线能最适宜描述褐煤基材料对Cd~(2+)的吸附特征。     

钼矿开采对球囊霉素相关土壤蛋白和土壤化学计量特性的影响

以不同开采程度钼矿区根际土壤为研究对象，探索了钼矿开采对土壤球囊霉素相关土壤蛋白、化学计量特性及其两者之间关系的影响。结果表明，开采区土壤碳、氮含量分别为25.30和1.00 g/kg，显著低于恢复区和未开采区土壤的碳、氮含量。开采区土壤的碳氮比达到29.36，分别是恢复区和未开采区的2.02倍和1.30倍。恢复区和未开采区土壤的总提取球囊霉素含量为2.81和3.64 mg/g，易提取球囊霉素含量为1.22和2.02 mg/g，分别是开采区土壤总提取和易提取球囊霉素的2.08倍、2.70倍和1.97倍、3.26倍。此外，土壤碳、氮含量对丛枝菌根真菌分泌球囊霉素相关土壤蛋白有显著的影响。可见，钼矿开采主要导致了土壤碳、氮的大量流失，并对丛枝菌根真菌分泌球囊霉素相关土壤蛋白具有明显的抑制作用。     

A Geochemical Equilibrium Modeling Approach to Assessing Soil Acidification Impacts Due to Depositions of Industrial Air Emissions

Soil acidification impacts arising from depositions of industrial air emissions may become a serious environmental concern. Currently, in the literature quantitative mechanistic modeling and the experimental acid neutralizing capacity (ANC) approach and a qualitative evaluation approach classifying soils into various levels of sensitivity to acid additions have been reported to assess the long-term soil acidification impacts due to industrial air emissions. Another alternative quantitative approach proposed by this study is the geochemical modeling approach that can be used to similate an ANC curve based on relevant soil chemistry data by calculating the equilibrium distributions of chemical species in the soil solution according to the specified geochemical processes. The purpose of this syudy was essentially to illustrate the potential applications and practical utility of the proposed geochemical modeling approach to assessing soil acidification impacts due to industrial air emissions. The application of the geochemical modeling apprach was illustrated by comparisons of the experimental and simulated ANC curves for a calcareous and a noncalcareous soil representing insensitive and sensitive soil cases, respectively. Results obtained from these comparisons reveal that, in terms of producing the ANC curve for the soil solution, the geochemical modeling approach seems to perform well and produce more reliable results for calcareous soil than for noncalcareous soil. However, the approach can also be used for noncalcareous soils when the air emission rates are low and may need further testing with additional measured data for a wide range of soils other than those presented in this study.     

山东主要果园土壤的粘土矿物组成及其吸附特性

研究了山东主要果园土壤中粘土矿物的组成、类型及其对P、K和Cu、Zn、Pb金属元素的吸附特性。结果表明：山东主要果园土壤的粘土矿物类型存在着明显的差异,淋溶较强,酸度较大的棕壤（简育湿润淋溶土）中粘土矿物以高岭石占优势,对P的吸附较强,但对K＋吸附固定较弱。含游离C aCO3较高的潮土（淡色潮湿雏形土）和褐土（简育干润淋溶土）,对P有较强的吸附和沉淀作用,使土壤磷的有效性降低。而砂姜黑土（钙积潮湿变性土）由于含有较高的蒙脱石和1.4 nm过渡矿物,对K＋具有很强的吸附和晶穴固定作用,因此砂姜黑土中磷肥和钾肥的有效性均较低,在施肥上应采取集中施肥和保持较湿润土壤环境等措施,以提高养分有效性。砂姜黑土和潮土对Cu、Zn、Pb金属元素的吸附显著地大于棕壤和褐土,主要的影响因素是不同土壤的粘粒含量和粘土矿物的类型的差异。同一土壤对Pb的吸附量远远大于对Zn和Cu的吸附量,主要取决于金属元素本身的化学性质和胶体的吸附特性。