玉米秸秆对Cr（VI）表观吸附过程的研究

玉米秸秆是一种重要的有机物料，它能通过表观吸附过程(包括物理吸附和化学反应过程)降低Cr(VI)污染。本试验采用间歇振荡法，初步研究了玉米秸秆对Cr(vi)的表观吸附动力学和等温线，并用吸附方程进行拟合。结果表明：玉米秸秆对Cr(vi)的表观吸附动力学以一级动力学方程为最优方程；表观吸附等温线可用Freundlich、Langmuir和Temkin方程描述，而以Freundlich方程的拟合效果最好；土壤或水体中的Cr(VI)含量越高，玉米秸秆的修复效果越差。     

不同来源生物炭对土壤磷吸附解吸的影响

主要研究了水稻秸秆、小麦秸秆、玉米秸秆、花生壳四种来源的生物炭对土壤磷吸附解吸的影响。研究结果表明:生物炭对土壤磷吸附的影响取决于土壤溶液中磷的浓度,与对照相比,在中低磷浓度(0~90 mg L-1)时,四种生物炭对土壤磷的吸附影响较小,而在较高磷浓度时,小麦秸秆生物炭和花生壳生物炭均抑制了土壤磷的吸附,而水稻秸秆生物炭和玉米秸秆生物炭均能促进土壤磷的吸附。吸附动力学试验表明,在反应开始的4小时内,土壤对磷的吸附较快,吸附量基本达到平衡吸附量的50%;到达吸附平衡时,添加生物炭能够降低土壤对磷的吸附量,四种生物炭对土壤磷的吸附量依次为:小麦秸秆玉米秸秆花生壳水稻秸秆。此外四种生物炭都能促进土壤中磷的解吸,其中玉米秸秆的促进效果最为显著,解吸量比对照高1.76倍。Langmuir方程和Freundlich方程都能很好地拟合生物炭存在下土壤磷的吸附等温线(P0.01),Freundlich拟合程度要比Langmuir方程的高。准一级动力学方程和准二级动力学方程都能很好地描述生物炭存在下土壤磷的吸附动力学(P0.01)。     

秸秆和硫酸铝改良剂对苏打盐碱土吸附腐殖酸性能的影响

为了揭示硫酸铝改良剂对苏打盐碱土在秸秆还田条件下固碳性能的影响,研究了添加秸秆和硫酸铝并于恒温条件下培养300天后的盐碱土对腐殖酸的吸附性能。结果表明:在腐殖酸吸附动力学中,秸秆和硫酸铝不同添加量条件下,盐碱土对腐殖酸的吸附均在120min时达到平衡,准二级动力学方程拟合效果最好,R2值最高(0.936)。Langmuir方程和Freundlich方程均可较好地拟合盐碱土对腐殖酸的等温吸附。添加相同比例的玉米秸秆条件下,Langmuir方程拟合获得的最大吸附量分别表现为69.335,42.830,40.498,42.593mg/g。而添加同等比例的硫酸铝改良剂条件下,最大吸附量分别表现为21.358,32.647,69.335,49.232,62.375,42.830mg/g。     

不同生物质炭对棕壤中磷素吸附解吸的影响

为了减少土壤磷素流失,提高磷肥利用效率,探究不同生物炭对棕壤中磷素吸附解吸行为的影响规律,以水稻秸秆、玉米秸秆和花生壳为原材料,利用限氧升温炭化法制备生物炭,通过批量吸附实验研究了生物炭种类和生物炭添加量对棕壤磷吸附解吸的影响。结果表明：水稻秸秆生物炭在添加量为0.4%时显著提高棕壤对磷的吸附量,花生壳生物炭和玉米秸秆生物炭则显著降低棕壤对磷的吸附量；等温吸附曲线表明,不同生物炭均未改变等温吸附曲线的变化趋势,均可用Langmuir方程和 Freundlich 方程进行描述(R²>0.93),其中 Langmuir 方程拟合效果更好,不同处理对磷的理论吸附量大小顺序为：水稻秸秆生物炭+棕壤>棕壤>花生壳生物炭+棕壤>玉米秸秆生物炭+棕壤；吸附动力学实验表明,不同生物炭均未改变磷吸附动力学曲线的变化趋势,在所有动力学模型中,准二级动力学模型最适合描述土壤对磷的吸附行为(R²>0.99),其次为准一级动力模型(R²>0.99)和Elovich动力学模型(R²>0.88)；三种生物炭均显著促进棕壤对磷的解吸,当生物炭添加量为≥0.2%时,水稻秸秆生物炭、玉米秸秆生物炭和花生壳生物炭,分别可提高棕壤对磷的解析率50%、70%和90%以上。由此可见,不同生物炭可提高棕壤对磷素的供应和利用,水稻秸秆生物炭在减少棕壤磷素流失、保护生态环境方面具有更大的应用价值。     

不同土壤对Cr吸附的动力学特征

该文采用振荡平衡法比较了来自中国15个省区16种土壤对Cr(Ⅵ)的吸附及其动力学特性,并探讨了土壤pH值、阳离了交换量、黏粒含量和有机质对Cr(Ⅵ)吸附及其动力学参数的影响.结果表明:具有较低土壤pH值和较高物理黏粒含量的土壤对Cr(Ⅵ)具有较人的表观吸附量,而土壤阳离子交换量和有机质因素对土壤Cr(Ⅵ)的表观吸附量影响较小.酸性土壤对Cr(Ⅵ)吸附能力较强,可以采用一级动力学方程和抛物线方程描述Cr(Ⅵ)在酸性土壤中的动力学行为,且土壤的表观吸附速率和平衡时的吸附量与土壤的pH值呈显著(p<0.05)负相关关系,而与物理黏粒含量旱显著(p<0.01)正相关关系;而碱性土壤对Cr(Ⅵ)吸附能力较小,很难用动力学方程描述其吸附动力学特性.可见,土壤pH值不仅影响土壤对Cr(Ⅵ)的表观吸附量,并且对Cr(Ⅵ)表观吸附动力学特征产生了较大影响.     

生物改性玉米秸秆处理含铜废水的研究

为解决水体中铜离子污染治理及玉米秸秆资源化利用等问题,以黑曲霉为改性菌剂,采用固态发酵法改性玉米秸秆,制备出复合生物吸附剂。采用傅里叶红外光谱仪(FT-IR)和扫描电子显微镜(SEM)表征改性玉米秸秆,同时对吸附剂的投加量(0.05～0.30 g)、溶液初始浓度(10～200 mg·L~(-1))、溶液初始pH(1.0～6.0)以及动力学和等温吸附线进行了研究。结果表明,通过黑曲霉固态发酵法改性后的玉米秸秆对Cu(Ⅱ)的饱和吸附量为33.6 mg·g~(-1),是天然玉米秸秆的2.65倍。FT-IR和SEM表征结果显示,改性材料表面空隙增多,更为粗糙,更多的活性基团得以暴露,这为吸附性能的提高提供了依据。改性玉米秸秆对Cu(Ⅱ)吸附30 min后达平衡,可用准二级动力学模型较好地拟合,吸附等温线符合Langmuir方程,该吸附过程以单分子层吸附为主。利用黑曲霉固态发酵技术改性玉米秸秆,是一种快速资源化处理玉米秸秆的方法。     

溶液初始pH值及裂解温度对玉米秸秆基生物炭吸附Cr(Ⅵ)的影响

以玉米秸秆为原料,在300、450℃和600℃下裂解得到3种生物炭,通过批处理实验讨论了溶液初始pH值和裂解温度对玉米秸秆及其生物炭吸附Cr(Ⅵ)的影响,并用吸附动力学模型和等温吸附模型对实验结果进行拟合。结果表明:对于同种吸附材料而言,溶液初始pH值越低,玉米秸秆及其生物炭对Cr(Ⅵ)的吸附量越大;当溶液初始pH值为3或5时,对Cr(Ⅵ)的吸附性能大小顺序为:玉米秸秆生物炭300℃生物炭450℃生物炭600℃;当溶液初始pH=1时,对Cr(Ⅵ)的吸附性能大小顺序为:生物炭300℃玉米秸秆生物炭450℃生物炭600℃,且生物炭300℃对Cr(Ⅵ)的最大吸附量约为141.24 mg·g~(-1)。可见,溶液初始pH值越低,生物炭的裂解温度越低,越有利于生物炭对Cr(Ⅵ)的吸附。     

小麦秸秆生物质炭的结构特征及其对Cr(VI)的吸附性能研究

以小麦秸秆为原料,在300℃和500℃下制备生物质炭（WS300和WS500）,对其性质进行表征,并研究其对Cr （VI）的吸附特性。结果表明随制备温度升高,生物质炭的C含量升高,缩合度增强,极性和亲水性减弱。WS500有更大的比表面积和孔容。Cr （VI）主要以HCrO₄^-和Cr₂O₇^2-的形态吸附在生物质炭表面。WS500有更为丰富的羟基、羧基、酯基等官能团,可与Cr （VI）发生络合、氧化还原等作用。Cr （VI）的吸附等温线更适合用Langmuir模型拟合,说明吸附主要是单分子层吸附。Cr （VI）在WS500上的吸附容量高于WS300。     

小麦秸秆生物炭对高氯代苯的吸附过程与机制研究

以小麦秸秆为原料,分别在三种温度(400℃、500℃、600℃)下制备小麦秸秆生物炭,并标记为WSB400、WSB500、WSB600。分析了秸秆炭的元素组成,表征了其结构和表面特征,研究了秸秆炭对五氯苯和六氯苯的吸附动力学和吸附等温线。结果表明,升温热解使得小麦秸秆有机组分炭化、极性官能团消除,炭化程度增强;三种秸秆炭均可快速高效地吸附高氯代苯,且对六氯苯的吸附要快于五氯苯,假二级动力学方程能更好地拟合秸秆炭对氯苯的吸附动力学过程;不同秸秆炭对氯苯的饱和吸附量大小顺序为WSB400WSB500WSB600;对吸附等温线进行分析可得,随着秸秆炭制备温度的升高,其对氯苯的吸附等温曲线由线性变为非线性,吸附机理则由以分配作用为主过渡到分配作用与表面吸附共同作用。     

热裂解温度对生物质炭吸附解吸Cd~(2+)行为的影响

以玉米秸秆、水稻秸秆、稻壳为原料分别在350℃、450℃、550℃、650℃热裂解温度下制备玉米秸秆炭(MSB)、水稻秸秆炭(RSB)和稻壳炭(RHB),比较不同热裂解温度下三种生物质炭对溶液中重金属离子Cd~(2+)的吸附解吸特性。利用准一级、准二级和颗粒内扩散模型对吸附过程进行拟合,结果表明三种生物质炭对Cd~(2+)的吸附满足颗粒内扩散方程。随着热裂解温度的升高,同一种原料制备的生物质炭达到吸附平衡的时间缩短。Langmuir方程和Freundlich方程拟合结果显示,三种生物质炭对溶液中Cd~(2+)的吸附更符合Langmuir方程。单位数量的RSB在一定浓度Cd~(2+)溶液中对Cd~(2+)的吸附量显著高于MSB和RHB。三种生物质炭对Cd~(2+)的吸附量随制备生物质炭的热裂解温度的升高而降低。三种生物质炭中玉米秸秆炭的解吸率最小。因此评价生物质炭对溶液中重金属的去除效果需要考虑原料、热裂解温度等多种因素的影响。     

Biosorption of Chromium (III) and Chromium (VI) by Untreated and Pretreated Cassia fistula Biomass from Aqueous Solutions

The present study explained the effect of pretreatments on the biosorption of Cr (III) and Cr (VI) by Cassia fistula biomass from aqueous solutions. For this purpose Cassia fistula biomass was pretreated physically by heating, autoclaving, boiling and chemically with sodium hydroxide, formaldehyde, gluteraldehyde, acetic acid, hydrogen peroxide, commercial laundry detergent, orthophosphoric, sulphuric acid, nitric acid, and hydrochloric acid. The adsorption capacity of biomass for Cr (III) and Cr (VI) was found to be significantly improved by the treatments of gluteraldehyde (95.41 and 96.21 mg/g) and benzene (85.71 and 90.81 mg/g) respectively. The adsorption capacity was found to depend on pH, initial metal concentration, dose, size, kinetics, and temperature. Maximum adsorption of both the Cr (III) and Cr (VI) was observed at pH 5 and 2. When Freundlich and Langmuir isotherms were tested, the latter had a better fit with the experimental data. The kinetic studies showed that the sorption rates could be described better by a second order expression than by a more commonly applied Lagergren equation.     

Validation of an electrothermal atomization atomic absorption spectrometry method for quantification of total chromium and chromium(VI) in wild mushrooms and underlying soils

An ETAAS method was validated to quantify total Cr and Cr(VI) in mushrooms and the underlying soils. The method includes a sample pretreatment for total Cr dissolution using a wet acid digestion procedure and a selective alkaline extraction for Cr(VI). The limits of detection were, expressed in microg/L, 0.15 and 0.17 for total Cr and Cr(VI), respectively. The linearity ranges under the optimized conditions were 0.15-25.0 and 0.17-20.0 microg/L for total Cr and Cr(VI), respectively. The limits of quantification were, expressed in microg/g of dry weight, 0.0163 and 0.0085 for total and hexavalent chromium, respectively. The precision of the instrumental method for total Cr and Cr(VI) was lower than 1.6%, and for the analytical method, it was lower than 10%. The accuracy of the method for Cr(VI) quantification was evaluated by the standard additions method, with the recoveries being higher than 90% for all of the added concentrations. For total Cr, certified reference materials (lichen CRM 482 and soil sample NCS ZC73001) were used. An interference study was also carried out in a mushroom simulated matrix, and it was verified that the deviations of the expected values were lower than 4.0% for both total Cr and Cr(VI). The validated method was applied to the evaluation of total Cr and Cr(VI) in 34 wild mushrooms and 34 respective underlying soil samples collected in two different regions of Portugal (Beira Interior and TrAs-os-Montes), with different locations regarded as noncontaminated or contaminated areas. The species were identified by a mycologist and subdivided into 10 genera and 15 species: Amanita (rubescens, muscaria, and ponderosa), Boletus (regius), Lactarius (deliciosus, vellereus, and piperatus), Suillus (granulatus and luteus), Tricholoma (acerbum), Agaricus (sylvicola), Volvariella (gloiocephala), Lecopaxillus (giganteus), Macrolepiota (procera), and Psilocybe (fascicularis). The mean values found for total Cr were 1.14 and 1.11 microg/g of dry weight, and for Cr(VI), the mean values were 0.103 and 0.143 microg/g of dry weight for cap and stalk, respectively. For soils, the mean concentrations found were, for total Cr, 84.0 microg/g and, for Cr(VI), 0.483 microg/g. The bioconcentration factors (BCFs) based on dry weight for cap and stalk were determined, and the values found, for both total Cr and Cr(VI), were always <1, although for hexavalent chromium, the BCFs were 10 times higher than for total chromium.     

铬与对氯苯胺的交互作用对其在土壤胶体上的反应的影响

Adsorption of Cr(VI) and p-chloroaniline on three typical soil colloids and pH influence were studied using batch equilibrium method.Both of Cr(VI) and p-chloroaniline adsorption on the colloids could be well described by general adsorption simulation equations,The adsorption processes changed with media pH.When Cr(VI) and p-chloroaniline coexisted on soil colloids,their interactions could be observed in a certain pH range to be accompanied with Cr(VI) reduction,which clearly suggested that a surface catalytic reaction occurred in this system.Soil colloid acted as an effcient catalyst for the interaction of Cr(VI)and p-chloroaniline.The pH values at which no interaction was observed were 4.0,4.5and 5.0 for the colloids of indigotic black soil,yellow-brown soil and latosol,respectively,Capillary electrophoresis used to analyze p-chloroaniline provided a high separation efficiency and short separation time,and needed no more extensive pretreatment of samples.     

茶树枝叶制备生物炭负载纳米零价铁净化水中Cr(VI)

茶树废弃物引起的环境破坏和病虫害爆发问题日益突出,对其进行无害化和资源化利用具有重要意义。该研究以修剪的茶树枝叶提取液作为还原剂和封端剂,以提取后的残渣作为炭源,成功制备了一种可高效去除水中六价铬(Cr(Ⅵ))的生物炭负载纳米零价铁复合材料(nanoscale zero-valent iron embedded tea leaves,TLBC-nZVI)。分析了材料用量、溶液初始pH值和温度等对Cr(Ⅵ)去除效果的影响;利用扫描电子显微镜结合能量色散X射线光谱仪(SEMEDS)、傅立叶变换红外光谱仪(FTIR)、X射线粉晶衍射仪(XRD)和X射线光电子能谱仪(XPS)等对材料进行表征,结合吸附动力学、吸附等温线和吸附热力试验探讨了去除机制。结果表明酸性条件、高温、增加材料用量有利于TLBC-nZVI对Cr(Ⅵ)的去除。TLBC-nZVI吸附过程符合准二级动力学模型、颗粒内扩散模型和Freundlich吸附等温模型,该吸附是自发的化学吸热过程。TLBC-nZVI与Cr(Ⅵ)的反应机制为吸附在材料上的Cr(Ⅵ)被零价铁(Fe⁰)和还原性官能团还原为三价铬(Cr(Ⅲ))...     

Kinetic, Isotherm and Thermodynamic Analysis on Adsorption of Cr(VI) Ions from Aqueous Solutions by Synthesis and Characterization of Magnetic-Poly(divinylbenzene-vinylimidazole) Microbeads

The magnetic-poly(divinylbenzene-1-vinylimidazole) [m-poly(DVB-VIM)] microbeads (average diameter 53-212?μm) were synthesized and characterized; their use as adsorbent in removal of Cr(VI) ions from aqueous solutions was investigated. The m-poly(DVB-VIM) microbeads were prepared by copolymerizing of divinylbenzene (DVB) with 1-vinylimidazole (VIM). The m-poly(DVB-VIM) microbeads were characterized by N(2) adsorption/desorption isotherms, ESR, elemental analysis, scanning electron microscope (SEM) and swelling studies. At fixed solid/solution ratio the various factors affecting adsorption of Cr(VI) ions from aqueous solutions such as pH, initial concentration, contact time and temperature were analyzed. Langmuir, Freundlich and Dubinin-Radushkvich isotherms were used as the model adsorption equilibrium data. Langmuir isotherm model was the most adequate. The pseudo-first-order, pseudo-second-order, Ritch-second-order and intraparticle diffusion models were used to describe the adsorption kinetics. The apparent activation energy was found to be 5.024?kJ?mol(-1), which is characteristic of a chemically controlled reaction. The experimental data fitted to pseudo-second-order kinetic. The study of temperature effect was quantified by calculating various thermodynamic parameters such as Gibbs free energy, enthalpy and entropy changes. The thermodynamic parameters obtained indicated the endothermic nature of adsorption of Cr(VI) ions. Morever, after the use in adsorption, the m-poly(DVB-VIM) microbeads with paramagnetic property were separeted via the applied magnetic force. The magnetic beads could be desorbed up to about 97% by treating with 1.0?M NaOH. These features make the m-poly(DVB-VIM) microbeads a potential candidate for support of Cr(VI) ions removal under magnetic field.     

Studies on Adsorption Characteristics of Al-Free and Al-Substituted Goethite for Heavy Metal Ion Cr(VI)

In the present paper, α-FeOOH and α-Fe(Al)OOH were prepared, and the adsorption of Cr(VI) on the two samples was investigated. The influence of pH, initial concentration, and some anions such as SO₄ ^2?, H₂PO₄ ^?, C₂O₄ ^2?, CO₃ ^2?, and SiO₃ ^2? on the adsorption of Cr(VI) on α-FeOOH and α-Fe(Al)OOH was studied by batch techniques. The results show that the adsorption capacity of Cr(VI) on α-Fe(Al)OOH increases with the introduction of aluminum, but decreases with the increase of pH. The adsorption irreversibility of Cr(VI) on α-Fe(Al)OOH is much higher than that on pure α-FeOOH. The adsorbed Cr(VI) species mainly exists in the form of *Fe(wk)-OHCrO₄ ^2? on the surface of the samples. With the presence of SiO₃ ^2?, CO₃ ^2?, C₂O₄ ^2?, SO₄ ^2?, and H₂PO₄ ^?, the binding of Cr(VI) is inhibited by different degree. The inhibition of those anions is larger in the pure goethite than that in the Al-substituted goethite system. After Al was introduced into α-FeOOH, Cr(VI) ions are preferentially adsorbed on Al sites rather than Fe sites on α-Fe(Al)OOH.     

Removal of Hexavalent Chromium-Contaminated Water and Wastewater: A Review

Cr(VI) is a well-known highly toxic metal, considered a priority pollutant. Industrial sources of Cr(VI) include leather tanning, cooling tower blowdown, plating, electroplating, anodizing baths, rinse waters, etc. This article includes a survey of removal techniques for Cr(VI)-contaminated aqueous solutions. A particular focus is given to adsorption, membrane filtration, ion exchange, and electrochemical treatment methods. The primary objective of this article is to provide recent information about the most widely used techniques for Cr(VI) removal.     

Hydrogeochemical behavior of chromium in the unsaturated zone and in the aquifer of leon valley,Mexico

The ground water of Leon valley, Central Mexico, is contaminated with chromium. A study was carried out to determine the main physico-chemical interactions between chromium and the aquifer solid matrix in the most polluted area. Five boreholes, 30 m deep, were drilled and used as piezometers. Unaltered solid cores were analyzed for Cr(VI), total Cr, Fe and Mn. Cr(VI) was determined in the water from the piezometers. We conclude that reduction of Cr(VI) by iron is important, adsorption of Cr(VI) by sand and gravel layers is negligible, and adsorption by silt and clay layers is significant in the saturated and unsaturated zones. In the saturated zone hexavalent chromium distributes preferentially in the water phase oxidation of chromium by manganese was not detected. A correlation between chromium, manganese and iron concentrations was observed for the aquifer solid matrix in this area, when the source of chromium was not anthropogenic.     

Kinetic Study of the Effect of pH on Hexavalent and Trivalent Chromium Removal from Aqueous Solution by <Emphasis Type="Italic">Cupressus lusitanica</Emphasis> Bark

Solution pH is among the most important parameters that influence heavy metal biosorption. This work presents a kinetic study of the effects of pH on chromium biosorption onto Cupressus lusitanica Mill bark from aqueous Cr(VI) or Cr(III) solutions and proposes a mechanism of adsorption. At all assayed contact times, the optimum pH for chromium biosorption from the Cr(III) solution was 5.0; in contrast, optimum pH for chromium biosorption from the Cr(VI) solution varied depending on contact time. The kinetic models that satisfactorily described the chromium biosorption processes from the Cr(III) and Cr(VI) solutions were the Elovich and pseudo second-order models, respectively. Diffuse reflectance infrared Fourier transform spectroscopy studies suggest that phenolic compounds present on C. lusitanica Mill bark play an important role in chromium biosorption from the Cr(III) solution. On the other hand, chromium biosorption from the Cr(VI) solution involved carboxyl groups produced on the bark by redox reactions between oxygen-containing groups and Cr(VI), and these were in turn responsible for the biosorption of Cr(III) produced by Cr(VI) reduction.     

Influence of Increasing Soil Copper Concentration on the Susceptibility of Phosphomonoesterase and Urease to Heat Disturbance

The sorption of chromium (Cr) species to soil has become the focus of research as it dictates the bioavailability and also the magnitude of toxicity of Cr. The sorption of two environmentally important Cr species [Cr(III) and Cr(VI)] was examined using batch sorption, and the data were fitted to Langmuir and Freundlich adsorption isotherms. The effects of soil properties such as pH, CEC, organic matter (OM), clay, water-extractable SO₄ ^2– and PO₄ ^3–, surface charge, and different iron (Fe) fractions of 12 different Australian representative soils on the sorption, and mobility of Cr(III) and Cr(VI) were examined. The amount of sorption as shown by K _f was higher for Cr(III) than Cr(VI) in all tested soils. Further, the amount of Cr(III) sorbed increased with an increase in pH, CEC, clay, and OM of soils. Conversely, the chemical properties of soil such as positive charge and Fe (crystalline) had a noticeable influence on the sorption of Cr(VI). Desorption of Cr(VI) occurred rapidly and was greater than desorption of Cr(III) in soils. The mobility of Cr species as estimated by the retardation factor was higher for Cr(VI) than for Cr(III) in all tested soils. These results concurred with the results from leaching experiments which showed higher leaching of Cr(VI) than Cr(III) in both acidic and alkaline soils indicating the higher mobility of Cr(VI) in a wide range of soils. This study demonstrated that Cr(VI) is more mobile and will be bioavailable in soils regardless of soil properties and if not remediated may eventually pose a severe threat to biota.