毒死蜱在不同土壤腐殖酸上的吸附/解吸特征

通过平衡振荡法研究毒死蜱在不同来源土壤腐殖酸(Has)上的吸附/解吸行为.结果表明,毒死蜱在Has上的等温吸附行为用Freundlich模型描述相对更合理;它们的吸附等温线在实验范围内基本呈直线,且吸附能力很强,顺序为:紫色潮土Has＞黄壤Has＞中性紫色土Has＞酸性紫色土Has＞腐殖土Has;但毒死蜱的解吸率较小,其值均小于26.70%,有明显的滞后现象,尤其是腐殖土Has和紫色潮土Has,固定能力顺序为:紫色潮土Has＞腐殖土Has＞中性紫色土Has＞酸性紫色土Has＞黄壤Has.由于不同来源土壤中Has的组成结构差异明显,它们对毒死蜱的吸附/解吸规律表现出不同的特征.土壤Has对毒死蜱的吸附/解吸行为的影响是多种因素综合作用的结果,具体作用机理尚待进一步研究.     

Enhanced removal of tetracycline via advanced oxidation of sodium persulfate and biochar adsorption

Advanced oxidation of antibiotic tetracycline (TC) is becoming an accessible and efficient technology. The removal of TC from the complex wastewater needs to be lucubrated. In this study, a TC removal system involving degradation and adsorption was established. TC degradation was accomplished by enhanced advanced oxidation via the addition of sodium persulfate (SP) and biochar into simulated wastewater containing Mn²⁺ and TC wastewater. The adsorption of TC and its derivatives was removed by biochar. The results indicate that the optimized reaction parameters were 3.0 g/L of biochar prepared at 600 °C (B600) and 400 mg/L of SP under acidic condition, and the removal percentage of TC was 87.48%, including 74.23% of degradation and 13.28% of adsorption; the anions Cl^?, NO₃^?, and H₂PO₄^? had negligible effects on the removal of TC in this Mn²⁺/B600/SP system. The system also functioned well with an aqueous solution with a high chemical oxygen demand (COD) concentration. Electron paramagnetic resonance (EPR) analysis indicated that ·OH and SO₄^? free radicals were present in the Mn²⁺/B600/SP system. Based on the testing and analysis results, a removal mechanism and potential TC degradation pathway for this system were proposed. TC can be degraded by ·OH and SO₄^? via three degradation pathways. Mn²⁺ can be precipitated as MnO₂, and a part of the TC and its derivatives can be adsorbed on the biochar surface. The Mn²⁺/B600/SP system also performed satisfactorily for a complex aqueous solution with various cations and antibiotics.

     

Enhanced desorption of RDX from granular activated carbon.

Several methods (cosolvents, surfactants, and cyclodextrins) were compared for improving desorption of a high explosive, RDX, from granular activated carbon (GAC). In batch desorption tests, 3% of the adsorbed RDX (initially 71.1 mg RDX/g GAC) was desorbed by water over 11 days, compared to 92.6% desorption by 100% ethanol. Solutions of ethanol or methanol in water also effectively desorbed RDX, although methanol was somewhat less effective than ethanol. Sodium dodecyl sulfate desorbed as much as 70% of the adsorbed RDX, while the non-ionic surfactants Tween 80, Triton X-100, and Brij 30 desorbed as much as 42 to 51% of the RDX. In continuous flow column tests, GAC was partially regenerated. One-half of the adsorbed RDX was desorbed by 2100 bed volumes (BV) of 10% ethanol, compared to the 22 500 BV of buffered water. Column modeling indicated that competitive adsorption and altered equilibrium conditions combined to enhance RDX desorption.     

Photochemical formation of hydroxyl radicals catalyzed by montmorillonite

In this work, the photooxidation of benzene and the formation of phenol in aqueous suspensions of the iron-rich montmorillonite under irradiation of a 250W metal halide lamp (lambda> or = 365nm) were investigated. We confirmed that hydroxyl radicals (()OH) were produced by illuminating montmorillonite and was responsible for the photooxidation of benzene in aqueous suspensions of montmorillonite. Low pH value facilitated the formation of hydroxyl radicals in the pH range of 2.0-10.0. The ()OH concentration increased with increasing the concentration of montmorillonite in aqueous solutions in the range of 0-20.0gl(-1). Higher concentration like 25.0gl(-1) montmorillonite inhibited the ()OH production. Iron, predominantly free iron in the clays, is believed to be one of the most important factors determining ()OH formation. Structural irons in montmorillonite have contributions to ()OH formation, especially in the presence of carboxylate ions. The formation of ()OH from montmorillonite under irradiation of near UV and visible light indicates that clays might play important role not only in transfer through adsorption but also in transformation through oxidation of organic compounds on the surface of clay particles in air, water, soil or even top sediments.     

Desorption of cadmium from goethite: effects of pH, temperature and aging

Cadmium is perhaps environmentally the most significant heavy metal in soils. Bioavailability, remobilization and fate of Cd entering in soils are usually controlled by adsorption-desorption reactions on Fe oxides. Adsorption of Cd on soil colloids including Fe oxides has been extensively studied but Cd desorption from such soil minerals has received relatively little attention. Some factors that affect Cd adsorption on goethite include pH, temperature, aging, type of index cations, Cd concentrations, solution ionic strength and presence of organic and inorganic ions. This research was conducted to study the influence of pH, temperature and aging on Cd desorption from goethite. Batch experiments were conducted to evaluate Cd desorption from goethite with 0.01 M Ca(NO3)2. In these experiments Cd desorption was observed at 20, 40 and 70 degrees C in combination with aging for 16 h, 30, 90 and 180 d from goethite that adsorbed Cd from solutions containing initial Cd concentrations of 20, 80 and 180 microM. Following the adsorption step Cd desorption was measured by 15 successive desorptions after aging at various temperatures. At the lowest amount of initially adsorbed Cd and equilibrium pH 5.5, cumulative Cd desorption decreased from 71% to 17% with aging from 16 h to 180 d and the corresponding decrease at equilibrium pH 6.0 was from 32% to 3%. There was a substantial decrease in Cd desorption with increasing equilibration temperature. For example, in goethite with the lowest amount of initial adsorption at equilibrium pH 5.5, cumulative Cd desorption decreased from 71% to 31% with increase in temperature from 20 to 70 degrees C, even after 16 h. Dissolution of Cd adsorbed goethite in 1M HCl, after 15 successive desorptions with 0.01 M Ca(NO3)2, indicated that approximately 60% of the Cd was surface adsorbed. Overall, dissolution kinetics data revealed that 23% to 88% Cd could not be desorbed, which could possibly be diffused into the cracks and got entrapped in goethite crystals. At elevated temperature increased equilibrium solution pH favoured the formation of CaCO3 and CdCO3 which reasonably decreased Cd desorption. Cadmium speciation showed the formation of calcite and otavite minerals at 40 and 70 degrees C due to increase in pH (>9.5) during aging. X-ray diffraction analysis (XRD) of these samples also revealed the formation of CaCO3 at elevated temperatures with aging. While mechanisms such as Cd diffusion and/or entrapment into fissures and cracks in goethite structure with increase in temperature and aging are possible.     

土霉素在4种人工湿地基质上的吸附-解吸特性

为了研究土霉素在人工湿地基质床中的行为机制,本实验采用批量平衡方法研究了壤土、煤灰渣、粗砂和细砂等4种人工湿地基质材料对土霉素的吸附、解吸特性。结果表明,土霉素在人工湿地基质材料上的吸附可分为前4小时的快速吸附阶段和之后的慢速吸附阶段,14 h后达到吸附平衡,这一吸附平衡时间明显低于一般人工湿地系统的水力停留时间。可以认为,土霉素在人工湿地中有足够的时间吸附于基质层上,其吸附量的大小主要取决于基质材料的性质。土霉素在4种基质材料上的等温吸附实验表明,吸附等温线均呈非线性,用Freundlich方程能较好地对吸附数据进行非线性拟合。在4种人工湿地基质材料中,煤灰渣对土霉素的吸附作用最强,通过Freundlich方程拟合的吸附容量参数(KF)为280.2;其次为壤土,KF值为129.3;粗砂和细砂的吸附作用较弱,KF值分别为53.2和64.5。人工湿地基质材料对土霉素的吸附能力主要与基质有机质含量、粘粒含量、Fe2O3含量、阳离子交换量和Al2O3含量呈正相关。土霉素在4种人工湿地基质材料上的解吸均存在滞后现象,相对于壤土和煤灰渣,吸附于粗砂和细砂上的土霉素更容易被解吸下来。     

Reactive oxygen species responsible for the enhanced desorption of dodecane in modified Fenton's systems.

The enhanced treatment of sorbed contaminants has been documented in modified Fenton's reactions; contaminants are desorbed and degraded more rapidly than they desorb by fill-and-draw or gas-purge desorption. The reactive species responsible for this process was investigated using dodecane as a model sorbent. Hydroxyl radical, hydroperoxide anion, and superoxide radical anion were generated separately to evaluate their roles in enhanced dodecane desorption. Dodecane desorption from silica sand over 180 minutes was negligible in gas-purge systems and in the hydroxyl radical and hydroperoxide anion systems. In contrast, enhanced desorption of dodecane occurred in superoxide systems, with >80% desorption over 180 minutes. Scavenging of superoxide eliminated the enhanced desorption of dodecane in both superoxide and modified Fenton's systems, confirming that superoxide is the desorbing agent in modified Fenton's reactions. Conditions that promote superoxide generation in Fenton's reactions may enhance their effectiveness for in situ subsurface remediation of sorbed hydrophobic contaminants.     

改性甘蔗渣对Cu2+和Zn2+的吸附机理

研究了均苯四甲酸二酐(PMDA)和乙二胺四乙酸二酐(EDTAD)改性甘蔗渣对重金属离子Cu2+和Zn2+的吸附性能,包括吸附动力学和吸附等温线。结果表明,改性后的甘蔗渣对重金属离子Cu2+和Zn2+的吸附容量有显著提高,对Cu2+和Zn2+吸附等温线均符合Langmuir方程,吸附为单分子层吸附。根据Langmuir方程,PMDA和EDTAD改性甘蔗渣对Cu2+的吸附量分别为60.21和33.45 mg/g,对Zn2+的吸附量分别是70.53和36.53 mg/g。两种改性甘蔗渣对两种金属离子的吸附在30 min内均可完成,用准二级吸附动力学方程模拟动力学过程得到较好的线性相关性。以EDTA溶液为洗脱剂对吸附Cu2+和Zn2+的改性甘蔗渣进行洗脱再生,再生的吸附剂可反复使用。     

改性多壁碳纳米管对水中Cd2+的去除

为了增加多壁碳纳米管(multiwall carbon nanotubers,MWNTs)对水中Cd2+的吸附量,使用混酸对多壁碳纳米管进行氧化处理,采用红外光谱进行结果表征,并探讨了吸附时间、pH值和MWNTs的使用量、Cd2+的浓度及干扰离子对镉离子吸附的影响。结果表明,吸附时间为1.5 h、pH为5.3、吸附效果最佳,随MWNTs量的增加Cd2+去除量增加,共存的阳离子会降低对Cd2+的吸附效果,对Cd2+的吸附符合Longmuir吸附定律。研究同时表明,pH小于2时Cd2+能容易从碳纳米管上解吸。初步探讨了Cd2+吸附机制。     

Phosphate removal and recovery with a synthetic hydrotalcite as an adsorbent

Phosphate removal is important to control eutrophication and an ion exchange process is one of several treatment processes for this purpose. Hydrotalcite compounds (HTALs) are useful as adsorbents for phosphate removal because of their ion exchange properties. In this study, the adsorption properties of a granular synthetic HTAL for phosphate and the method of regeneration of the granular HTAL were examined. The adsorption isotherm of the granular HTAL was approximated by a modified Langmuir type, and the maximum adsorption capacity was 47.3 mg P g(-1), which corresponded to the content of HTAL in the granular one. Phosphate adsorbed on the HTAL was effectively desorbed with alkaline NaCl solutions and the HTAL was regenerated with 25 w/v% MgCl(2) solution. The regenerated HTAL could be reused repeatedly for the phosphate removal. Phosphate in the exhausted desorption solution was recovered as a precipitate of calcium phosphate by addition of CaCl(2), and the residual exhausted desorption solution could be also reused after supplying NaOH. The results suggest the possibility of an effective system for phosphate removal and recovery, which includes the following processes: adsorption, desorption, recovery of phosphate, and regeneration of the HTAL and the desorption solution.     

Cadmium adsorption and desorption behaviour on goethite at low equilibrium concentrations: effects of pH and index cations

The transport and bioavailability of cadmium is governed mainly by its adsorption-desorption reactions with minerals such as goethite--a common iron oxide mineral in variable charged and highly weathered tropical soils. Soil factors such as pH, temperature, solution Cd concentration, ionic strength and ageing affect Cd adsorption on goethite. The desorption behaviour of Cd from goethite at low concentrations is not fully understood. This study investigates the adsorption-desorption of Cd at low Cd concentrations (Cd adsorbed on goethite from 20 to 300 microM Cd solutions) in Na and Ca nitrate solutions of 0.03 M nominal ionic strengths. Synthetic goethite prepared by ageing a ferric hydroxide gel at high pH and room temperature was used for Cd adsorption and desorption studies. For desorption experiment 10 successive desorptions were made for the whole range of initial Cd concentrations (20-300 microM) in the presence of 0.01 M Ca(NO3)2 or 0.03 M NaNO3 solutions. Cadmium adsorption was found to be higher in Na+ than Ca2+ probably due to the competition of Ca2+ ions with Cd2+ ions for adsorption sites on the surfaces of goethite. The effect of index cation on Cd adsorption diminished with increase in pH from 5.0 to 6.0. Cadmium desorption decreased with increase in pH from 5.0 to 6.0 in both Na and Ca systems. After 10 successive desorptions with 0.03 M NaNO3 at the lowest initially adsorbed Cd approximately 45%, 20% and 7% of the adsorbed Cd was desorbed at pH 5.0, 5.5 and 6.0, respectively. The corresponding desorptions in the presence of 0.01 M Ca(NO3)2 were 49%, 22% and 8%, respectively. The Freundlich parameter, k, based on each progressive step of desorption at different adsorbed concentration increased with increasing desorption step, which may indicates that a fraction of Cd was resistant to desorption. Low Cd desorbability from goethite may be due to its specific adsorption and/or possibly as a result of Cd entrapment in the cracks or defects in goethite structure.     

Hydroxyl radical concentration profile in photo-Fenton oxidation process: generation and consumption of hydroxyl radicals during the discoloration of azo-dye Orange II

Dynamic behaviors of hydroxyl (OH) radical generation and consumption in photo-Fenton oxidation process were investigated by measuring OH radical concentration during the discoloration of azo-dye Orange II. The effects of operating parameters for photo-Fenton discoloration, i.e. dosages of H₂O₂ and Fe, initial dye concentration, solution pH and UV irradiation, on the generation and consumption of OH radicals playing the main role in advanced oxidation processes were extensively studied. The scavenger probe or trapping technique in which coumarin is scavenger of OH radical was applied to estimate OH radical concentration in the photoreactor during the photo-Fenton discoloration process. The OH radical generation was enhanced with increasing the dosages of Fenton regents, H₂O₂ and Fe. At the initial stage of photo-Fenton discoloration of Orange II, the OH radical concentration rapidly increased (Phase-I) and the OH radical concentration decreased after reaching of OH radical concentration at maximum value (Phase-II). The decrease in OH radical concentration started when the complete discoloration of Orange II was nearly achieved and the H₂O₂ concentration became rather low. The dynamic behavior of OH radical concentration during the discoloration of Orange II was found to be strongly linked with the change in H₂O₂ concentration. The generation of OH radical was maximum at solution pH of 3.0 and decreased with an increase of solution pH. The OH radical generation rate in the Fenton Process was rather slower than that in the photo-Fenton process.     

Homogeneous degradation of 1,2,9,10-tetrachlorodecane in aqueous solutions using hydrogen peroxide, iron and UV light

The homogeneous degradation of the polychlorinated n-alkane, 1,2,9,10-tetrachlorodecane (T4C10), was studied in aqueous solutions of hydrogen peroxide, including Fenton and photo-Fenton reaction conditions. All solutions were adjusted to a pH of 2.8 and an ionic strength of 0.1 M NaClO4 prior to photolysis. T4C10 (2 x 10(-6) M) was substantially degraded by the H2O2/UV system (1.0 x 10(-2) M H2O2), with 60% disappearance in 20 min of irradiation in a photoreactor equipped with 300 nm lamps of light intensity 3.6 x 10(-5) Ein L(-1) min(-1) (established by ferrioxalate actinometry). The reaction produced stoichiometric amounts of chloride ion indicating complete dechlorination of the chlorinated n-alkane. T4C10 degraded very slowly under Fenton (Fe2+/H2O2/dark) and Fenton-like (Fe3+/H2O2/dark) conditions. However, when the same solutions were irradiated, T4C10 degraded more rapidly than in the H2O2/UV system, with 61% disappearance in 10 min of exposure. The rapid degradation is related to the enhanced degradation of hydrogen peroxide to oxidizing *OH radicals under photo-Fenton conditions. Degradation was inhibited in both the H2O2/UV and photo-Fenton systems by the addition of KI and tert-butyl alcohol due to *OH scavenging.     

改性花生壳对Cd(Ⅱ)和Pb(Ⅱ)的吸附机理

以前期制得改性块状花生壳为对象,测定改性花生壳等电点,考察离子强度对改性花生壳吸附Cd2+和Pb2+的影响、吸附前后吸附质溶液pH变化情况及蒸馏水、NaCl、HNO3、柠檬酸和EDTA 5种解吸液对Cd2+和Pb2+的解吸效果,并通过X-射线光电子能谱仪和傅里叶变换红外光谱仪对吸附前后的改性花生壳进行表征,推测并证实了改性花生壳对Cd2+和Pb2+可能的吸附机理。结果表明,改性花生壳对Cd2+和Pb2+可能的吸附机理是:Cd2+是通过外层络合、离子交换和内层络合的联合作用被吸附的;Pb2+主要是与改性花生壳上的O、N等活性基团发生内层络合;此外,改性花生壳表面生成的二氧化锰对Cd2+和Pb2+的吸附也起到一定的作用。     

Modification of carbon-coated TiO2 by iron to increase adsorptivity and photoactivity for phenol

Carbon-coated TiO(2) modified by iron, were prepared from TiO(2) of anatase structure and PET modified by FeC(2)O(4). Catalysts were prepared by mixing powders of TiO(2) and modified PET and heating at different temperatures, from 400 to 800 degrees C under flow of Ar gas. High adsorption of phenol was observed on the catalyst heated at 400 degrees C, confirmed by FT-IR analysis. On this catalyst, fast rate of phenol decomposition was achieved by addition of small amount of H(2)O(2) to the reaction mixture. Phenol decomposition proceeded mainly through the direct oxidation of phenol species adsorbed on the catalyst surface due to the photo-Fenton reaction. Iron-modified carbon-coated TiO(2) catalysts heated at 500-800 degrees C showed almost no phenol adsorption or oxidation.     

粘土矿物与重金属界面反应的研究进展

介绍了3种粘土吸附剂:蒙脱石、高岭石和伊利石对重金属的吸附、脱附等界面反应机理,以及粘土矿物对重金属的选择性及对吸附的影响因素.另外,还探讨了为提高其吸附性能而进行的改性方法.     

改性多壁碳纳米管对水中Cd~（2＋）的去除

为了增加多壁碳纳米管（multiwall carbon nanotubers,MWNTs）对水中Cd2＋的吸附量,使用混酸对多壁碳纳米管进行氧化处理,采用红外光谱进行结果表征,并探讨了吸附时间、pH值和MWNTs的使用量、Cd2＋的浓度及干扰离子对镉离子吸附的影响。结果表明,吸附时间为1.5 h、pH为5.3、吸附效果最佳,随MWNTs量的增加Cd2＋去除量增加,共存的阳离子会降低对Cd2＋的吸附效果,对Cd2＋的吸附符合Longmuir吸附定律。研究同时表明,pH小于2时Cd2＋能容易从碳纳米管上解吸。初步探讨了Cd2＋吸附机制。     

Effects of organic acids on adsorption of lead onto montmorillonite,goethite and humic acid

Adsorption isotherms for Pb onto six soil components (quartz, feldspar, kaolinite, montmorillonite, goethite and humic acid) were studied. The influence of pH, EDTA and citric acid on the adsorption of Pb onto montmorillonite, goethite and humic acid were considered. Results indicate that the experimental data fit the Langmuir Adsorption Isotherm. The adsorption capacity for Pb at pH 6 was found to be in the order: humic acid (22.7 mg g(-1)) > goethite (11.04 mg g(-1)) > montmorillonite (10.4 mg g(-1)) > kaolinite (0.91 mg g(-1)) > feldspar (0.503 mg g(-1)) > quartz (0.148 mg g(-1)). Generally, the amount of Pb adsorbed onto montmorillonite, goethite and humic acid decreased with increasing concentrations of EDTA and citric acid and with increases in alkality. However, there were two exceptions: (1) addition of citric acid increased the amount of Pb adsorbed onto humic acid; and (2) the amount of Pb adsorbed onto goethite decreased with increasing pH in the presence of EDTA. Some mechanisms involved in the adsorption reactions are discussed.     

改性甘蔗渣对Cu^2＋和Zn^2＋的吸附机理

研究了均苯四甲酸二酐（PMDA）和乙二胺四乙酸二酐（EDTAD）改性甘蔗渣对重金属离子Cu^2＋和Zn^2＋的吸附性能，包括吸附动力学和吸附等温线。结果表明，改性后的甘蔗渣对重金属离子Cu^2＋和Zn^2＋的吸附容量有显著提高，对Cu^2＋和Zn^2＋吸附等温线均符合Langmuir方程，吸附为单分子层吸附。根据Langmuir方程，PMDA和EDTAD改性甘蔗渣对Cu^2＋的吸附量分别为60．21和33．45mg／g，对Zn^2＋的吸附量分别是70．53和36．53mg／g。两种改性甘蔗渣对两种金属离子的吸附在30min内均可完成，用准二级吸附动力学方程模拟动力学过程得到较好的线性相关性。以EDTA溶液为洗脱剂对吸附Cu^2＋和Zn^2＋的改性甘蔗渣进行洗脱再生，再生的吸附剂可反复使用。     

Facile synthesis of cadmium-doped graphite carbon nitride for photocatalytic degradation of tetracycline under visible light irradiation

In recent years, using semiconductor photocatalysts for antibiotic contaminant degradation under visible light has become a hot topic. Herein, a novel and ingenious cadmium-doped graphite phase carbon nitride (Cd-g-C₃N₄) photocatalyst was successfully constructed via the thermal polymerization method. Experimental and characterization results revealed that cadmium (Cd) was well doped at the g-C₃N₄ surface and exhibited high intercontact with g-C₃N₄. Additionally, the introduction of cadmium significantly improved the photocatalytic activity, and the optimum degradation efficiency of tetracycline (TC) reached 98.1%, which was exceeded 2.0 times that of g-C₃N₄ (43.9%). Meanwhile, the Cd-doped sample presented a higher efficiency of electrical conductivity, light absorption property, and photogenerated electron-hole pair migration compared with g-C₃N₄. Additionally, the quenching experiments and electron spin-resonance tests exhibited that holes (h⁺), hydroxyl radicals (?OH), superoxide radicals (?O₂^?) were the main active species involved in TC degradation. The effects of various conditions on photocatalytic degradation, such as pH, initial TC concentrations, and catalyst dosage, were also researched. Finally, the degradation mechanism was elaborated in detail. This work gives a reasonable point to synthesizing high-efficiency and economic metal-doped photocatalysts.