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1.
Surface characterization of maize-straw-derived biochars and their sorption performance for MTBE and benzene 总被引：2，自引：1，他引：1
Liwei Xiao Erping Bi Beibei Du Xiaoli Zhao Chen Xing 《Environmental Earth Sciences》2014,71(12):5195-5205
Biochars generated at various temperatures might show significant differences in sorption for organic contaminants. In this study, a series of biochars, generated from pyrolyzing maize straws at different temperatures, were systematically characterized. The characterization results showed that with increasing pyrolysis temperature, the surface areas, micropore areas and aromaticity of biochars were enhanced. Batch experiments were conducted to study methyl tert-butyl ether (MTBE) and benzene sorption to biochars. The results indicated that the sorption capacity of benzene to biochars was higher than that of MTBE. The higher pyrolyzed temperature of biochars resulted in a stronger sorption affinity for target compounds, and the dominant sorption mechanisms varied for biochars pyrolyzed at different temperatures. The sorption to biochars pyrolyzed at 700 and 800 °C performed a high adsorption capacity, which indicated that they might be a promising sorbent to remove MTBE and benzene from water. Biochar pyrolyzed at 400 °C showed transitional sorption mechanisms from partition to adsorption for MTBE and benzene. Pore-filling was a possible sorption mechanism to biochars pyrolyzed at high temperature. 相似文献
2.
高温后花岗岩力学性质及微孔隙结构特征研究 总被引：3，自引：1，他引：2
采用MTS815液压伺服试验系统及9310型微孔结构分析仪对花岗岩在温度作用下（常温～1 300 ℃）的宏观力学性质及微孔隙结构特征进行了较为系统的研究。结果表明：①在800 ℃之前,岩样力学性质变化规律不明显;超过800 ℃,岩样强度迅速劣化;达到1 200 ℃,岩样基本失去了承载能力。②岩样孔隙率随温度升高而增大,孔隙率的阀值温度在800 ℃左右,与岩样在该温度点强度突然降低相一致。③岩样孔隙率较小,但连通性好,在阶段进汞曲线上显示为不同宽度微裂隙并存的特征,累计进汞曲线呈台阶状,温度超过800 ℃,超微孔逐渐向微孔隙转化,岩样连通性增强。④岩样孔隙分布分形维数随温度的升高反而降低。在高温作用下,岩样中的热损伤由初始非规则的裂隙结构逐渐向均匀化的孔穴结构转化,非均匀性弱化是导致岩样孔隙分布分形维数降低的根本原因。 相似文献
3.
Kinetics and Equilibrium Sorption Studies of 4-Nitrophenol on pyrolyzed and activated oil shale residue 总被引：1，自引：0，他引：1
Sorption of the organic pollutant 4-nitrophenol (4-NP) by pyrolyzed and activated Jordanian oil-shale was studied. Pyrolyzed oil shale was prepared using a fluidized bed reactor at 520 °C in the presence of nitrogen. Physical activation was carried out by treating the pyrolyzed oil shale with CO2 at 830 °C, while chemical activation was achieved by using KOH and ZnCl2 as impregnating agents. Batch kinetics and isotherm studies were conducted to evaluate the sorption process. Effects of contact time, initial sorbate concentration, sorbent concentration, temperature, pH and inorganic salts (NaCl and KCl) on the sorption process by the different sorbents were considered. Chemically activated oil shale, pretreated with ZnCl2, gave the highest uptake of 4-NP. The isotherm experimental data fit reasonably well to Langmuir, Freundlich and Redlich-Paterson models. Three kinetic models, namely the Morris-Weber, Lagergren, and Pseudo-Second-Order model (PSOM), were applied to represent the experimental results for both pyrolyzed and ZnCl2-oil shale sorbents. 相似文献
4.
Molecular dynamics (MD) computer simulations of liquid water held in one-dimensional nano-confinement by two parallel, electrostatically neutral but hydrophilic surfaces of brucite, Mg(OH)2, provide greatly increased, atomistically detailed understanding of surface-related effects on the spatial variation in the structural ordering, hydrogen bond (H-bond) organization, and local density of H2O molecules at this important model hydroxide surface. NVT-ensemble MD simulations (i.e., at constant number of atoms, volume and temperature) were performed for a series of model systems consisting of 3 to 30 Å-thick water layers (containing 35 to 360 H2O molecules) confined between two 19 Å-thick brucite substrate layers. The results show that the hydrophilic substrate significantly influences the near-surface water structure, with both H-bond donation to the surface oxygen atoms and H-bond acceptance from the surface hydrogen atoms in the first surface layer of H2O molecules playing key roles. Profiles of oxygen and hydrogen atomic density and H2O dipole orientation show significant deviation from the corresponding structural properties of bulk water to distances as large as 15 Å (∼5 molecular water layers) from the surface, with the local structural environment varying significantly with the distance from the surface. The water molecules in the first layer at about 2.45 Å from the surface have a two-dimensional hexagonal arrangement parallel to brucite layers, reflecting the brucite surface structure, have total nearest neighbor coordinations of 5 or 6, and are significantly limited in their position and orientation. The greatest degree of the tetrahedral (ice-like) ordering occurs at about 4 Å from the surface. The translational and orientational ordering of H2O molecules in layers further from the surface become progressively more similar to those of bulk liquid water. A quantitative statistical analysis of the MD-generated instantaneous molecular configurations in terms of local density, molecular orientation, nearest neighbor coordination, and the structural details of the H-bonding network shows that the local structure of interfacial water at the brucite surface results from a combination of “hard wall” (geometric and confinement) effects, highly directional H-bonding, and thermal motion. This structure does not resemble that of bulk water at ambient conditions or at elevated or reduced temperature, but shares some similarities with that of water under higher pressure. 相似文献
5.
Arsenate uptake by calcite: Macroscopic and spectroscopic characterization of adsorption and incorporation mechanisms 总被引：1，自引：0，他引：1
Batch uptake experiments and X-ray element mapping and spectroscopic techniques were used to investigate As(V) (arsenate) uptake mechanisms by calcite, including adsorption and coprecipitation. Batch sorption experiments in calcite-equilibrated suspensions (pH 8.3; PCO2 = 10−3.5 atm) reveal rapid initial sorption to calcite, with sorption rate gradually decreasing with time as available sorption sites decrease. An As(V)-calcite sorption isotherm determined after 24 h equilibration exhibits Langmuir-like behavior up to As concentrations of 300 μM. Maximum distribution coefficient values (Kd), derived from a best fit to a Langmuir model, are ∼190 L kg−1.Calcite single crystals grown in the presence of As(V) show well-developed rhombohedral morphology with characteristic growth hillocks on surfaces at low As(V) concentrations (?5 μM), but habit modification is evident at As(V) concentrations ?30 μM in the form of macrostep development preferentially on the − vicinal surfaces of growth hillocks. Micro-X-ray fluorescence element mapping of surfaces shows preferential incorporation of As in the − vicinal faces relative to + vicinals. EXAFS fit results for both adsorption and coprecipitation samples confirm that As occurs in the 5+ oxidation state in tetrahedral coordination with oxygen, i.e., as arsenate. For adsorption samples, As(V) forms inner-sphere surface complexes via corner-sharing with Ca octahedra. As(V) coprecipitated with calcite substitutes in carbonate sites but with As off-centered, as indicated by two Ca shells, and with likely disruption of local structure. The results indicate that As(V) interacts strongly with the calcite surface, similar to often-cited analog phosphate, and uptake can occur via both adsorption and coprecipitation reactions. Therefore, calcite may be effective for partial removal of dissolved arsenate from aquatic and soil systems. 相似文献
6.
Infrared spectroscopic and X-ray diffraction characterization of the nature of adsorbed arsenate on ferrihydrite 总被引：4，自引：0，他引：4
Fourier transformed infrared (FTIR) spectroscopy was used to characterize arsenate-ferrihydrite sorption solids synthesized at pH 3-8. The speciation of sorbed arsenate was determined based on the As-O stretching vibration bands located at 650-950 cm−1 and O-H stretching vibration bands at 3000-3500 cm−1. The positions of the As-O and O-H stretching vibration bands changed with pH indicating that the nature of surface arsenate species on ferrihydrite was strongly pH dependent. Sorption density and synthesis media (sulfate vs. nitrate) had no appreciable effect. At acidic pH (3, 4), ferric arsenate surface precipitate formed on ferrihydrite and constituted the predominant surface arsenate species. X-ray diffraction (XRD) analyses of he sorption solids synthesized at elevated temperature (75 °C), pH 3 clearly showed the development of crystalline ferric arsenate (i.e. scorodite). In neutral and alkaline media (pH 7, 8), arsenate sorbed as a bidentate surface complex (in both protonated FeO2As(O)(OH)− and unprotonated forms). For the sorption systems in slightly acidic media (pH 5, 6), both ferric arsenate and surface complex were probably present on ferrihydrite. It was further determined that the incorporated sulfate in ferrihydrite during synthesis was substituted by arsenate and was more easily exchangeable with increasing pH. 相似文献
7.
Eu3+水合离子在纳米二氧化硅表面的吸附与结构 总被引：1，自引：0，他引：1
采用发射光谱研究了不同pH和不同Eu初始浓度条件下,Eu在纳米二氧化硅-水界面的吸附特征。研究发现,当pH低时,Eu在纳米二氧化硅表面的吸附很少,随着pH的增加,Eu在纳米二氧化硅表面的吸附急剧增加,当出〉6时,几乎所有Eu都被吸附。研究同时表明,吸附在纳米二氧化硅与水界面的Eu离子种类也取决于pH值：当pH〈5时,吸附的Eu主要为Eu^3＋水合离子,当pH〉5时,吸附的Eu主要为Eu（CO3）^＋,甚至Eu（CO3）2^-离子。吸附的机理除了静电吸引外,更重要的是这些离子与纳米二氧化硅表面形成化学键,即表面化学吸附。 相似文献
8.
The sorption of Eu(III) onto kaolinite and montmorillonite was investigated up to 150 °C. The clays were purified samples, saturated with Na in the case of montmorillonite. Batch experiments were conducted at 25, 40, 80 and 150 °C in 0.5 M NaClO4 solutions to measure the distribution coefficients (Kd) of Eu as a trace element (<10−6 mol/L) between the solution and kaolinite. For the Na-montmorillonite, we used Kd results from a previous study [Tertre, E., Berger, G., Castet, S., Loubet, M., Giffaut, E., 2005. Experimental study of adsorption of Ni2+, Cs+ and Ln3+ onto Na-montmorillonite up to 150 °C. Geochim. Cosmochim. Acta69, 4937-4948] obtained under exactly the same conditions. The number and nature of the Eu species sorbed onto both clay minerals were investigated by time resolved laser fluorescence spectroscopy (TRLFS) in specific experiments in the same temperature range. We identified a unique inner-sphere complex linked to the aluminol sites in both clays, assumed to be AlOEu2+ at the edge of the particles, and a second exchangeable outer-sphere complex for montmorillonite, probably in an interlayer position. The Kd values were used to adjust the parameters of a surface complexation model (DLM: diffuse layer model) from 25 to 150 °C. The number of Eu complexes and the stoichiometry of reactions were constrained by TRLFS. The acidity constants of the amphoteric aluminol sites were taken from another study [Tertre, E., Castet, S., Berger, G., Loubet, M., Giffaut, E. Acid/base surface chemistry of kaolinite and Na-montmorillonite at 25 and 60 °C: experimental study and modelling. Geochim. Cosmochim. Acta, in press], which integrates the influence of the negative structural charge of clays on the acid/base properties of edge sites as a function of temperature and ionic strength. The results of the modelling show that the observed shift of the sorption edge towards low pH with increasing temperature results solely from the contribution of the AlOEu2+ edge complexes. Finally, we successfully tested the performance of our model by confronting the predictions with experimental Kd data. We used our own data obtained at lower ionic strength (previous study) or higher suspension density and higher starting concentration (TRLFS runs, this study), as well as published data from other experimental studies [Bradbury, M.H., Baeyens, B., 2002. Sorption of Eu on Na and Ca-montmorillonite: experimental investigations and modeling with cation exchange and surface complexation. Geochim. Cosmochim. Acta66, 2325-2334; Kowal-Fouchard, A., 2002. Etude des mécanismes de rétention des ions U(IV) et Eu(III) sur les argiles: influence des silicates. Ph.D. Thesis, Université Paris Sud, France, 330p]. 相似文献
9.
Djaafar Rehrah Rishipal R. Bansode Osman Hassan Mohamed Ahmedna 《International Journal of Environmental Science and Technology》2018,15(5):1093-1102
Qatar economy has been growing rapidly during the last two decades during which waste generation and greenhouse gas emissions increased exponentially making them among the main environmental challenges facing the country. Production of biochar from municipal solid organic wastes (SOWs) for soil application may offer a sustainable waste management strategy while improving crop productivity and sequestering carbon. This study was conducted to (1) investigate the physicochemical parameters of biochars for SOW, (2) select the best-performing biochars for soil fertility, and (3) evaluate the potential benefits of these biochars in lowering greenhouse gases (GHGs) during soil incubation. Biochars were produced from SOW at pyrolysis temperatures of 300–750 °C and residence times of 2–6 h. Biochars were characterized before use in soil incubation to select the best-performing treatment and evaluation of potential GHG-lowering effect using CO2 emission as proxy. Here, soil–biochar mixtures (0–2%w/w) were incubated in greenhouse settings for 120 days at 10% soil moisture. Soil properties, such as pH, EC, TC, and WHC, were significantly improved after soil amendment with biochar. Two biochars produced from mixed materials at 300–500 °C for 2 h and used at 0.5–1% application rate performed the best in enhancing soil fertility parameters. A significant decrease in CO2 emission was observed in vials with soil–biochar mixtures, especially for biochars produced at 500 °C compared the corresponding raw materials which exhibited an exponential increase in the CO2 emission. Hence, application of biochar to agricultural soils could be beneficial for simultaneously improving soil fertility/crop productivity while sequestering carbon, thereby reducing anthropogenic emissions of GHGs. 相似文献
10.
M.P.W. Schneider T. Scheel P. van Hees K. Kalbitz 《Geochimica et cosmochimica acta》2010,74(5):1606-3154
Amorphous Al hydroxides (am-Al(OH)3) strongly sorb and by this means likely protect dissolved organic matter (OM) against microbial decay in soils. We carried out batch sorption experiments (pH 4.5; 40 mg organic C L−1) with OM extracted from organic horizons under a Norway spruce and a European beech forest. The stabilization of OM by sorption was analyzed by comparing the CO2 mineralized during the incubation of sorbed and non-sorbed OM. The mineralization of OM was evaluated based in terms of (i) the availability of the am-Al(OH)3, thus surface OM loadings, (ii) spectral properties of OM, and (iii) the presence of phosphate as a competitor for OM. This was done by varying the solid-to-solution ratio (SSR = 0.02-1.2 g L−1) during sorption. At low SSRs, hence limited am-Al(OH)3 availability, only small portions of dissolved OM were sorbed; for OM from Oa horizons, the mineralization of the sorbed fraction exceeded that of the original dissolved OM. The likely reason is competition with phosphate for sorption sites favouring the formation of weak mineral-organic bindings and the surface accumulation of N-rich, less aromatic and less complex OM. This small fraction controlled the mineralization of sorbed OM even at higher SSRs. At higher SSRs, i.e., with am-Al(OH)3 more available, competition of phosphate decreased and aromatic compounds were sorbed selectively, which resulted in pronounced resistance of sorbed OM against decay. The combined OC mineralization of sorbed and non-sorbed OM was 12-65% less than that of the original DOM. Sorbed OM contributed only little to the overall OC mineralization. Stabilization of OC increased in direct proportion to am-Al(OH)3 availability, despite constant aromatic C (∼30%). The strong stabilization at higher mineral availability is primarily governed by strong Al-OM bonds formed under less competitive conditions. Due to these strong bonds and the resulting strong stabilization, the surface loading, a proxy for the mineral’s occupation by OM, was not a factor in the mineralization of sorbed OM over a wide range of C sorption (0.2-1.1 mg C m−2). This study demonstrates that sorption to am-Al(OH)3 results in stabilization of OM. The mineral availability as well as the inorganic solution chemistry control sorptive interactions, thereby the properties of sorbed OM, and the stability of OM against microbial decay. 相似文献
11.
河套干旱地区夏季边界层结构特征观测分析 总被引：2，自引：0，他引：2
利用2013年夏季7月爱尔达K/LLX802J型机动式边界层风廓线雷达获取的三维风场资料和银川站高空气象探测资料,对河套干旱地区夏季边界层日变化特征进行了分析.结果表明:爱尔达K/LLX802J型机动式风廓线雷达能较好的反映并分辨出夏季河套干旱地区边界层内大气湍流和风场的演变过程.夏季7月河套干旱地区边界层高度白天平均为2127.2 m,夜间平均为1760.7 m,白天边界层高度比夜间平均高366.5 m.河套干旱区夏季地表非绝热加热对边界层的影响主要集中在800 m以下,800~2000 m高度边界层则主要受昼夜交替和大尺度天气系统的影响.夏季7月河套干旱地区边界层风速在300 m以下随高度增加而增大,离地500 m以下边界层易在北京时间07:00-11:00和18:00-21:00时段发生风速切变;300 m以下边界层白天盛行西南偏南风、夜间盛行南风,300~2000 m高度边界层白天和夜间均盛行东南风;离地300 m以下边界层易在夜间21:00-23:00时出现风向切变.夏季7月白天河套干旱地区边界层大气垂直速度在300 m高度以下随高度增加而增大,由0.3 m·s-1增大到0.6 m·s-1,夜间边界层大气垂直速度在200 m高度以下随高度增大而增大;300 m高度以上边界层大气垂直速度无论昼夜随高度变化均较小. 相似文献
12.
Yassaman Babaee Catherine N. Mulligan Md. Saifur Rahaman 《Environmental Earth Sciences》2017,76(19):650
Due to the severity of arsenic contamination of soil and water resources around the world, finding new adsorbents for arsenic removal from the water is of high importance. The present study investigates the possible use and effectiveness of starch-stabilized Fe/Cu nanoparticles for adsorption of arsenic from aqueous solutions. First, Fe/Cu nanoparticles at various starch concentrations of 0, 0.02, 0.04 and 0.06 wt% were synthesized and characterized by X-ray diffraction, transmission electron microscopy and zeta potential/particle size analyzer. Then 0.04 wt% stabilized Fe/Cu nanoparticles were tested for the sorption of As(III) and As(V) from synthetic arsenic-contaminated water. To have an understanding about the arsenic adsorption mechanism of nanoparticles, X-ray photoelectron spectroscopy (XPS) was performed before and after adsorption. The results showed that starch provides nanoparticles with a neutral surface and stabilization of nanoparticles is possible with 0.04 wt% or higher concentrations of starch. For 0.04 wt% starch-stabilized Fe/Cu nanoparticles, the adsorption isotherms fit well within the Langmuir equation, with maximum sorption capacities of 90.1 mg/g for As(III) and 126.58 mg/g for As(V) at a pH of 7.0 from the aqueous arsenic solutions. Examining the XPS spectra of nanoparticles before and after adsorption showed that arsenic adsorption by this nanoparticle can be due to the formation of inner-sphere arsenic complexes on the particle surface, and the surface oxygen-containing functional groups involved in adsorption. The high sorption capacity suggests the potential for applying starch-stabilized Fe/Cu nanoparticles to the contaminated waters for removal of arsenic. 相似文献
13.
Bamidele I. Olu-Owolabi Paul N. Diagboya Chukwunonso P. Okoli Kayode O. Adebowale 《Environmental Earth Sciences》2016,75(24):1494
In order to predict exposure risks as well as appropriate remediation strategies for pesticides in soils, knowledge of pesticides sorption processes onto various representative soils is vital. Hence, laboratory batch experiments were carried out to study sorption of a pesticide, pentachlorophenol (PCP), on five soils obtained from different sub-Saharan agro-ecological zones (AEZs) in order to understand sorption equilibrium, kinetics, and thermodynamics. Experimental data showed that sorption equilibrium was attained within 24 h. The fitting of kinetic results and equilibrium data to different models suggested partly surface adsorption and partly partitioning of PCP within voids of the various soil components. Sorption was mainly attributed to sharing or exchange of valence electrons between negatively charged PCP molecules and positively charged soil sorption sites. The sorption process was spontaneous and accompanied by decreased entropy, but was pH and temperature dependent, reducing with increase in pH and temperature. The various soils’ PCP sorption capacities were directly proportional to their cation exchange capacities. The low PCP sorption observed in these soils suggested high risk of PCP being present in soil water solution, especially at higher temperatures, which can lead to contamination of the aquifer. This risk may be higher for soils obtained from AEZs with warmer natural temperatures. 相似文献
14.
The sorption of lead (II) and cadmium (II) on seven shales belonging to the Proterozoic Vindhyan basin, central India, and a black cotton soil, Mumbai, India, was studied and compared with sorbent geochemistry. The sorption equilibrium studies were conducted under completely mixed conditions in batch reactors (pH=5.0 and ionic strength= 0.01 M) at room temperature. The Freundlich model provided better fits to the experimental data compared to Langmuir model. High cadmium and lead sorption was observed for the calcareous shales with greater than 5% CaCO3. The Freundlich isotherm parameter relating to sorption capacity, i.e., KF, yielded a strong correlation with the calcium carbonate and calcium oxide content across the various geosorbents studied. The observed sorption pattern may be attributed to complex formation of CaCO3 with Pb2+ and Cd2+ leading to surface precipitation. Moreover, the Ca2+ present in the sorbents may also involve in ion exchange reaction with lead and cadmium. 相似文献
15.
Y. A. Londoño G. A. Peñuela 《International Journal of Environmental Science and Technology》2018,15(9):1887-1896
This study evaluated three types of pharmaceuticals and personal care products (methylparaben, ibuprofen and triclosan) at concentration levels of 300, 500, 1000 and 2000 µg/L by implementing batch tests using anaerobic processes and granular biomass. The study aimed to identify the mechanisms of biodegradation and sorption in the degradation of these compounds. The inoculum was granular sludge from a laboratory-scale anaerobic reactor. The characterization results of the inoculum showed an anaerobic biomass with high activity, good sedimentation and a high percentage of organic matter. The results of the removal of the pollutants showed high degradation percentages for methylparaben (close to 99%), with negligible sorption in the sludge. The results also showed insignificant ibuprofen sorption but removal close to 0%. Triclosan showed high biomass sorption and low biodegradation. In addition, at the concentrations tested, none of the compounds had a negative or inhibitory effect on the microbial populations of the system. 相似文献
16.
Bogdan Saletnik Grzegorz Zaguła Dorota Grabek-Lejko Idalia Kasprzyk Marcin Bajcar Maria Czernicka Czesław Puchalski 《Environmental Earth Sciences》2017,76(16):574
Because of their physicochemical properties, biochars can be used as sorption materials for removal of toxic substances. The purpose of the present study was to determine whether biochar obtained from cones of larch (Larix decidua Mill. subsp. decidua) and spruce (Picea abies L. H. Karst) could be used as a sorbent for Cd2+, Pb2+ and Co2+ in aqueous solutions. So far, this feedstock had not been tested in this respect. The material was subjected to pyrolysis at 500 and 600 °C for the duration of 5, 10 and 15 min. The obtained pyrolysates were found to differ in terms of pH and the contents of the essential macroelements. The different values of these parameters were determined for varying temperature, duration of the pyrolysis process and type of feedstock. Sorption capacities of the biochars for removal of Cd2+, Pb2+ and Co2+ were examined using simulated contamination of aqueous solutions with salts of these metals. The findings showed the highest, nearly complete, removal for Pb2+ were maximum 99.7%, and almost three times lower value for Cd2+ and Co2+ (respectively, 35.7 and 24.8%). It was demonstrated that pyrolysis of conifer cones produced optimum sorption capacities when the process was conducted at a temperature of 500 °C for the duration of 5 min. It was shown that products of spruce cone pyrolysis were characterized by better sorption capacity in comparison with products of larch cone pyrolysis. The properties of conifer cone biochar create the possibility of using it as an adsorbent in water and wastewater treatment as well as in production of filters and activated carbon. 相似文献
17.
Citrate impairs the micropore diffusion of phosphate into pure and C-coated goethite 总被引：1，自引：0，他引：1
Christian Mikutta Friederike Lang Martin Kaupenjohann 《Geochimica et cosmochimica acta》2006,70(3):595-607
Anions of polycarboxylic low-molecular-weight organic acids (LMWOA) compete with phosphate for sorption sites of hydrous Fe and Al oxides. To test whether the sorption of LMWOA anions decreases the accessibility of micropores (<2 nm) of goethite (α-FeOOH) for phosphate, we studied the kinetics of citrate-induced changes in microporosity and the phosphate sorption kinetics of synthetic goethite in the presence and absence of citrate in batch systems for 3 weeks (500 μM of each ion, pH 5). We also used C-coated goethite obtained after sorption of dissolved organic matter in order to simulate organic coatings in the soil. We analyzed our samples with N2 adsorption and electrophoretic mobility measurements. Citrate clogged the micropores of both adsorbents by up to 13% within 1 h of contact. The micropore volume decreased with increasing concentration and residence time of citrate. In the absence of citrate, phosphate diffused into micropores of the pure and C-coated goethite. The C coating (5.6 μmol C m−2) did not impair the intraparticle diffusion of phosphate. In the presence of citrate, the diffusion of phosphate into the micropores of both adsorbents was strongly impaired. We attribute this to the micropore clogging and the ligand-induced dissolution of goethite by citrate. While the diffusion limitation of phosphate by citrate was stronger when citrate was added before phosphate to pure goethite, the order of addition of both ions to C-coated goethite had only a minor effect on the intraparticle diffusion of phosphate. Micropore clogging and dissolution of microporous hydrous Fe and Al oxides may be regarded as potential strategies of plants to cope with phosphate deficiency in addition to ligand-exchange. 相似文献
18.
Batch experiments were conducted to study the sorption of uranium on selected clay minerals (KGa-1b and KGa-2 reference kaolinite,
SWy-2 and STx-1b reference montmorillonite, and IBECO natural bentonite) as a function of pH (4–9) and 0.001, 0.01, and 0.025 M
NaCl in equilibrium with the CO2 partial pressure of the atmosphere. Uranium concentrations were kept below 100 μg L−1 to avoid precipitation of amorphous Uranium-hydroxides. Solely PTFE containers and materials were used, because experiments
showed significant sorption at higher pH on glass ware. All batch experiments were performed over a period of 24 h, since
kinetic experiments proved that the common 10 or 15 min are in many cases by far not sufficient to reach equilibrium. Kaolinite
showed much greater uranium sorption than the other clay minerals due to the more aluminol sites available. Sorption on the
poorly crystallized KGa-2 was higher than on the well-crystallized KGa-1b. Uranium sorption on STx-1b and IBECO exhibited
parabolic behavior with a sorption maximum around pH 6.5. Sorption of uranium on montmorillonites showed a distinct dependency
on sodium concentrations because of the effective competition between uranyl and sodium ions, whereas less significant differences
in sorption were found for kaolinite. The presence of anatase as impurity in kaolinite enhanced the binding of uranyl-carbonate
complexes with surface sites. The kinetic of uranium sorption behavior was primarily dependent on the clay minerals and pH.
A multisite surface complexation model without assuming exchange is based on the binding of the most dominant uranium species
to aluminol and silanol edge sites of montmorillonite, respectively to aluminol and titanol surface sites of kaolinite. For
eight surface species, the log_k was determined from the experimental data using the parameter estimation code PEST together
with PHREEQC. 相似文献
19.
《Geochimica et cosmochimica acta》1999,63(19-20):2891-2901
A long-standing problem in aquatic geochemistry has been the incorporation of natural organic matter (NOM) into speciation models. The general effect of NOM on metal ion sorption by particles has been understood for some time, and significant progress has been made in elucidating some of the details of the role of NOM through the use of surrogate organic acids such as citric acid. However, a gap exists between the general observations that have been made of NOM behavior and the inclusion of NOM in surface chemical models for metal ion sorption. In this paper, we report on the results of a study on the sorption of U(VI) by hematite in the absence and presence of Suwannee river humic acid (HA) and over a range of other system conditions (e.g., pH, I). Essential HA characteristics (e.g., its acid/base, metal binding, and surface chemical properties) were “captured” by representing the HA as an assembly of monoprotic acids with assumed pK values and without explicit correction for electrostatic effects. The ternary system (hematite/HA/U(VI)) was simulated through the combination of the binary submodels (i.e., CO32−/hematite, U(VI)/HA, U(VI)/hematite, and HA/hematite) with model constants fixed at the values determined from simulations of the respective experimental systems. However, the “summed-binary” approach undersimulated experimental results, and the ternary system model required the postulation of two ternary surface (Type A) complexes composed of the uranyl ion, hematite surface sites, and the model ligands comprising the HA. Consideration of the HA in this manner permitted the simulation of HA effects on U(VI) sorption by hematite over a range of solution conditions using a general speciation model. 相似文献
20.
Christian Mikutta Jaane Krüger Friederike Lang 《Geochimica et cosmochimica acta》2006,70(12):2957-2969
Hydration of organic coatings in soils is expected to affect the sorption of oxyanions onto hydrous Fe and Al oxides. We hypothesized that the hydration of polygalacturonate (PGA) coatings on alumina (Al2O3) increases their permeability for phosphate. Pure and PGA-coated alumina were equilibrated in deionized water for 2 and 170 h at pH 5 and 20 °C before studying (i) their porosity with N2 gas adsorption and 1H NMR relaxometry, (ii) structural changes of PGA-coatings with differential scanning calorimetry (DSC), and (iii) the kinetics of phosphate sorption and PGA desorption in batch experiments. Scanning electron micrographs revealed that PGA molecules formed three-dimensional networks with pores ranging in size from <10 to several hundred nanometers. Our NMR results showed that the water content of intraparticle alumina pores decreased upon PGA sorption, indicating a displacement of pore water by PGA. The amount of water in interparticle alumina pores increased strongly after PGA addition, however, and was attributed to water in pores of PGA and/or in pores at the PGA-alumina interface. The flexibility of PGA molecules and the fraction of a PGA gel phase increased within one week of hydration, implying restructuring of PGA. Hydration of PGA coatings increased the amount of phosphate defined as instantaneously sorbed by 84%, showing that restructuring of PGA enhanced the accessibility of phosphate to external alumina surfaces. Despite the fact that the efficacy of phosphate to displace PGA was higher after 170 h than after 2 h, a higher phosphate surface loading was required after 170 h to set off PGA desorption. Our findings imply that the number of PGA chain segments directly attached to the alumina surface decreased with time. We conclude that hydration/dehydration of polymeric surface coatings affects the sorption kinetics of oxyanions, and may thus control the sorption and transport of solutes in soils. 相似文献