Preparations and properties of transformation products of pentachlorophenol (PCP)

The present paper describes preparations and properties of pentachlorophenol derivatives.     

Removal and recovery of uranium(VI) by adsorption onto a lignocellulosic-based polymeric adsorbent containing amidoxime chelating functional group

A new adsorbent (ABS) with amidoxime functional group was prepared through graft polymerization of acrylonitrile onto banana stem (BS) using ceric ammonium nitrate (CAN)/HNO₃ initiator system, followed by treatment with hydroxylamine hydrochloride in alkaline solution. Infrared spectroscopy, surface area analyzer, thermogravimetry, and potentiometric titration were used for the characterization of the adsorbent. Effective removal of U(VI) ions was demonstrated at the pH range 4.0–6.0. The mechanism for the removal of U(VI) ions by ABS was based on complexation adsorption model. Equilibrium was achieved in approximately 3 h. The experimental kinetic data were analyzed using first-order, second-order, and Elovich kinetic models, and are well fitted with second-order kinetics. The temperature dependence indicates an exothermic process. U(VI) adsorption was found to decrease with increase of ionic strength. The Freundlich isotherm model fitted the experimental equilibrium data well. The adsorption efficiency was tested using synthetic nuclear industry effluents. The maximum adsorption capacity for U(VI) removal was found to be 80 mg g^-1 at 20°C. Adsorbed U(VI) ions were desorbed effectively, about 99% by 0.2 M HCl. Repeated adsorption/desorption cycles show the feasibility of the ABS for the removal of U(VI) ions from water and nuclear industry effluents.     

磷酸盐在土壤中吸附与解吸研究进展

就国内外有关磷酸盐在土壤中的吸附与解吸的研究进行了简要的综述,重点是关于磷酸盐的吸附研究包括磷酸盐在土壤中吸附的数学模拟、土壤吸附磷酸盐的机制、影响磷酸盐吸附的土壤组分、磷酸盐在土壤中解吸及其与吸附的关系以及有机无机土壤改良剂对磷酸盐吸附的影响,并提出了有待进一步研究的问题。     

淹水还原作用下土壤镉的吸附与解吸特征的初步探讨

利用黄棕壤发育的水稻土(pH6.53),设置6个不同处理恒温(25±0.1)℃培养20d,初步探讨了3种还原强度土壤对Cd的吸附和解吸特征。试验数据显示:强度还原土壤,Eh和pH降低并稳定在-474mV和5.02水平,Cd吸附率由开始时的99.96%下降到94.70%,Cd解吸率平均为90.01%;中度还原土壤,Eh下降至-90mV左右,pH略有上升,Cd吸附率和解吸率平均分别为99.96%和66.09%;氧化态土壤的Eh、pH和Cd解吸率变化都比较小,平均分别为400.4mV、6.11和46.78%。此结果表明,处于不同还原状况下的土壤表面对Cd吸附和解吸有所差别;强度还原土壤对外源Cd的吸附率小于中度还原土壤对外源Cd的吸附率;土壤吸附外源Cd的解吸率,由大到小的次序依次为强度还原土壤,中度还原土壤,氧化状态土壤;还原程度越强,土壤对Cd的吸附率越低,Cd的解吸率也越高;还原条件下土壤Eh、pH、交换性亚铁和水溶性有机质含量是影响土壤Cd吸附和解吸的主要因素。     

Effects of organic acids on Cd adsorption and desorption by two anthropic soils

The objective of this experiment was to study the effects of malic, tartaric, oxalic, and citric acid on the adsorption and desorption characteristics of Cd by two typical anthropic soils (lou soil and irrigation-silted soil) in North-west China. Cadmium adsorption and desorption were studied under a range of temperatures (25°C, 30°C, 35°C, 40°C), organic acid concentrations (0.5–5.0 mmol·L^-1), and pH values (2–8). The results showed that the Cd adsorption capacity of the lou soil was significantly greater than that of the irrigation-silted soil. Generally, Cd adsorption increased as the temperature increased. In the presence of NaNO₃, the adsorption of Cd was endothermic with ΔH values of 31.365 kJ·mol^-1 for lou soil and 28.278?kJ·mol^-1 for irrigation-silted soil. The endothermic reaction indicated that H bonds were the main driving force for Cd adsorption in both soils. However, different concentrations of organic acids showed various influences on the two soils. In the presence of citric acid, chemical adsorption and van der Waals interactions were the main driving forces for Cd adsorption rather than H bonds. Although the types of organic acids and soil properties were different, the effects of the organic acids on the adsorption and desorption of Cd were similar in the two soils. The adsorption percentage of Cd generally decreased as organic acid concentrations increased. In contrast, the adsorption percentage increased as the pH of the initial solution increased. The exception was that adsorption percentage of Cd increased slightly as oxalic acid concentrations increased. In contrast, the desorption percentage of Cd increased with increasing concentrations of organic acids but decreased as the initial solution pH increased.     

Effective removal of Cobalt(II) ions from aqueous solutions and nuclear industry wastewater using sulfhydryl and carboxyl functionalised magnetite nanocellulose composite: batch adsorption studies

A new adsorbent sulfhydryl and carboxyl functionalized magnetite nanocellulose composite [(MB-IA)-g-MNCC] was synthesized by graft co-polymerization of itaconic acid onto magnetite nanocellulose (MNCC) using EGDMA as cross linking agent and K₂S₂O₈ as free radical initiator. The adsorption occurs maximum in the pH 6.5. The best fitted kinetic model was found to be pseudo-second-order kinetics. Therefore the mechanism of Co(II) adsorption onto (MB-IA)-g-MNCC follows ion exchange followed by complexation. The Langmuir model was the best fitted isotherm model for the adsorption of Co(II) onto the (MB-IA)-g-MNCC. Simulated nuclear power plant coolant water samples were also treated with (MB-IA)-g-MNCC to demonstrate its efficiency for the removal of Co(II) from aqueous solutions in the presence of other metal ions. To recover the adsorbed Co(II) ions and also to regenerate the adsorbent to its original state 0.1?M HCl was used as suitable desorbing agent. Six cycles of adsorption-desorption experiments were conducted and was found that adsorption capacity of (MB-IA)-g-MNCC has been decreased from 97.5% in the first cycle to 84.7% in the sixth cycle. Recovery of Co(II) using 0.1?M HCl decreased from 93.2% in the first cycle to 79.3% in the sixth cycle.

Abbreviations: T: absolute temperature; q_e: amount adsorbed at equilibrium; q_t: amount adsorbed at time t; CELL: cellulose; Co: cobalt; C_e: concentration at equilibrium; C_HCl: concentration of HCl; C_NaOH: concentration of NaOH; C_A: concentrations of acid; C_B: concentrations of base; W_g: dry weight of composite; W_i: dry weight of MNCC; DS: energy dispersive spectra; EGDMA: ethylene glycol dimethacrylate; Ce: equilibrium concentration; K_L: equilibrium constant; F: Faradays constant; FTIR: Fourier transform infrared spectra; ΔG^o: free energy change; K_F: Freundlich adsorption capacity; 1/n: Freundlich constant; R: gas constant; D: grafting density; EC_o: initial concentration; IA: itaconic acid; IA-g-MNCC: itaconic acid-grafted-magnetite nanocellulose composite; b: Langmuir constant; MNCC: magnetite nanocellulose composite; Q⁰: Maximum adsorption capacity; (MB-IA)-g-MNCC: 2-mercaptobenzamide modified itaconic acid-grafted-magnetite nanocellulose composite; NC: nanocellulose; pH_pzc: Point of zero charge; K₂S₂O₈: potassium peroxy sulphate; k₁: pseudo-first-order rate constant; k₂: pseudo-second-order rate constant; SEM: scanning Electron Microscope; b_s: Sips adsorption capacity; Q_s: Sips maximum adsorption capacity; ΔH°: standard enthalpy change; ΔS°: standard entropy change; A: surface area; σ₀: surface charge density; 1/n_s: surface heterogeneity factor; VSM: vibrating sample magnetometer; V: volume of solution; W: weight of (MB-IA)-g-MNCC; M_composite: weight of the composite; XRD: X-ray diffraction     

Removal of pentachlorophenol from contaminated soil by catalytic oxidation with iron(III)-porphyrin complexes and potassium monopersulfate

Pentachlorophenol (PCP) in contaminated soil was removed by treatment with aqueous solutions of iron(III)-porphyrin complexes as catalysts and potassium monopersulfate (KHSO₅) as the oxygen donor. The contaminated soils were artificially prepared by spiking PCP to the kaolin and ando soils. Three types of iron(III)-porphyrin complexes, tetra(?p-sulfophenyl) porphineiron(III) (Fe(III)-TPPS), tetra(N-methyl-4-pyridil)porphineiron(III) (Fe(III)-TMPyP) and heme, were examined, and Fe(III)-TPPS was found to be the most effective for removing PCP. Although the sequential addition of KHSO₅ was examined, in an attempt to improve the efficiency of PCP removal, it was not effective. In a preliminary test of various aqueous solutions, the addition of humic acid (HA), with a lower degree of humification, led to a significant enhancement in PCP removal. When HA was added to the soil system, the percentages of PCP removal were increased by up to 10% compared to the absence of HA. Therefore, the addition of HA to the catalytic system was useful in enhancing PCP removal from contaminated soil.     

Competitive adsorption and desorption of copper and lead in some soil of North China

The competitive adsorption and desorption of Pb(II) and Cu(II) ions in the soil of three sites in North China were investigated using single and binary metal solutions with 0.01 mol·L^-1 CaCl₂ as background electrolyte. The desorption isotherms of Pb(II) and Cu(II) were similar to the adsorption isotherms, which can be fitted well by Freundlich equation (R₂>0.96). The soil in the three sites had greater sorption capacities for Pb(II) than Cu(II), which was affected strongly by the soil characteristics. In the binary metal solution containing 1∶1 molar ratio of Pb(II) and Cu(II), the total amount of Pb(II) and Cu(II) adsorption was affected by the simultaneous presence of the two metal ions, indicating the existence of adsorption competition between the two metal ions. Fourier transform infrared (FT-IR) spectroscopy was used to investigate the interaction between soil and metal ions, and the results revealed that the carboxyl and hydroxyl groups in the soil were the main binding sites of metal ions.     

不同磷含量和秸秆添加量对褐土镉吸附解吸的影响

采用室内培养的方法,通过人为添加不同量的玉米干秸秆和磷,研究不同含磷量土壤对镉吸附解吸影响,以探讨磷—镉在土壤中的交互作用机制。结果表明,不同含磷量的土壤对不同质量浓度锌镉吸附解吸时,在低质量浓度镉（Cd3）条件下,土壤对镉的吸附量随磷质量分数的增加先升高后降低,解吸量随着土壤中磷质量分数的增加先升高后降低再升高;而在高质量浓度镉（Cd30）条件下,土壤对镉的吸附量随磷质量分数的增加逐渐升高,在相同磷水平下,随外加锌质量浓度的增加,镉的吸附量明显降低,而解吸量则逐渐升高。不同秸秆量土壤对不同质量浓度镉吸附解吸时,在Cd3条件下,土壤对镉的吸附量随秸秆加入量的增加先升高后降低,而在同一质量分数磷情况下,吸附量逐渐下降;土壤对镉的解吸量在磷质量分数为120 mg·kg^-1（P2）时最低,而后随着磷质量分数的增加而增加。在同一质量分数磷水平情况下,随着秸秆添加量的增加,土壤对镉的解吸量逐渐增加。而在Cd30条件下,土壤对镉的吸附量逐渐增加,在同一磷水平情况下,土壤对镉的吸附情况是低量秸秆（C1）〉高量秸秆（C2）,但在磷质量分数为240 mg·kg^-1（P3）水平下,不添加秸秆（C0）情况时镉的吸附量最大,而后降低。土壤对镉的解吸量随着磷含量的增加而增加。在同一磷水平情况下,随着秸秆添加量的增加,土壤对镉的解吸量逐渐增加。     

磷对褐土中锌镉次级吸附和解吸影响

通过吸附和解吸试验,研究了不同磷吸附量石灰性褐土对锌镉次级吸附和解吸的影响。结果表明,次级吸附锌和镉对不同吸附量磷土壤的磷解吸量随磷吸附量的增加而增加,而磷解吸量随次级吸附后锌、镉浓度的增加而降低,即随锌镉添加量的增加,磷的有效性有所降低。土壤对锌的次级吸附量和吸附率随磷吸附量的增加先降低后升高,并随添加镉浓度的增加而降低,解吸量和解吸率随磷吸附量的增加而增加,说明在正常施磷范围内,增加磷的施用量能提高土壤中锌的有效性,同时,土壤对高浓度锌的次级吸附率小于低浓度锌的次级吸附率,而土壤对高浓度锌的解吸量和解吸率要远大于对浓度锌的解吸量和解吸率;土壤对镉的次级吸附量、吸附率和解吸量、解吸率都随着磷吸附量的增加而增加,且吸附量随添加镉的量增加而增加,但镉次级吸附量和吸附率随添加锌浓度的增加而减小,解吸量和解吸率却增大,说明在磷吸附量相同的条件下,添加锌促进了镉的有效性。     

黄泥土微团聚体颗粒组对Cu2+的吸附与解吸研究

采用低能量超声波分散和冷冻机干燥法提取太湖地区黄泥土不同粒径微团聚体颗粒组样品,用平衡液吸附法和CaCl2与HCl溶液的连续解吸法研究原土和不同粒径微团聚体颗粒组对重金属Cu2 的吸附和解吸特征。结果表明,对于Cu2 的吸附,原土用Langmuir方程拟合最佳,而不同粒径微团聚体颗粒组用Freundlich方程拟合最佳。原土和不同粒径微团聚体颗粒组吸附量大小顺序为粘粒级>砂粒级>原土>粉砂级>粗粉砂级,这与其游离氧化铁和有机质含量呈显著正相关。原土和不同粒径微团聚体颗粒组对Cu2 的专性吸附质量分数随吸附量增加而减少,而非专性吸附质量分数则相反。不同粒径微团聚体颗粒组吸附总量小于原土,所以传统风干磨细的研究方法可能高估了土壤对铜固持能力。     

潮土中磷锌交互作用机制探讨及磷对锌吸附-解吸的影响

采用室内培养和吸附解吸两种方法,探讨了潮土中磷、锌交互作用机制。结果表明：土壤中DTPA提取态锌质量分数随添加锌量的增加而增加,低磷质量分数处理可提高土壤锌有效性,但高磷质量分数处理却降低了土壤锌的有效性;土壤速效磷质量分数均随锌添加量的增加而有所降低。在施锌25 mg.kg-1背景下,土壤中DTPA提取态锌质量分数随施磷质量分数的增加呈先增加后降低趋势,在添加磷量小于180 mg.kg-1时,土壤DTPA提取态锌质量分数显著地高于其他处理,但随添加磷量的增加,土壤DTPA提取态锌质量分数显著降低,当磷添加量大于540 mg.kg-1时,土壤DTPA提取态锌质量分数明显低于其他磷处理,说明当添加磷量小于180 mg.kg-1时,磷提高土壤中锌有效性的主要机制是二者竞争吸附土壤胶体表面吸附点位的竞争机制;当添加磷量大小540 mg.kg-1时,磷影响锌有效性的主要机制为沉淀作用。在土壤施磷量为180 mg.kg-1时,随添加锌质量分数的提高,土壤中速效磷质量分数呈先升高后降低趋势。吸附-解吸研究表明,随土壤中速效磷质量分数的提高（27.60~2773.86 mg.kg-1）,土壤对锌的吸附量先降低再增加,而KCl解吸的锌量却是先增加再降低。因此潮土中磷锌交互作用机制为,土壤中磷和锌质量分数均较低时,磷与锌有效性呈协同作用;当磷或锌质量分数过高时,协同作用减弱;磷和锌质量分数再增加二者的有效性将出现拮抗作用。     

Removal of congo red and basic violet 1 by chir pine (Pinus roxburghii) sawdust,a saw mill waste: batch and column studies

The efficiency of chir pine sawdust (CPS) for adsorptive removal of the dyes, congo red (CR) and basic violet 1 (BV), from aqueous solution was evaluated using batch and column studies. The equilibrium was attained in 60 min for CR and 45 min for BV. The adsorption of BV obeyed the Langmuir isotherm model while the Freundlich isotherm fitted the equilibrium data of CR adsorption. The Langmuir monolayer adsorption capacities (Q_o) of CPS for BV and CR were 11.3 and 5.8 g kg^?1, respectively. The kinetic data for CR were best fitted to the Lagergren pseudo-first-order model and for BV to the pseudo-second-order model. The intra-particle diffusion was found to be the rate-controlling step for CR adsorption, while the adsorption kinetics of BV were controlled by both intra-particle and liquid-film diffusion. The thermodynamic parameters indicated that the adsorption process was spontaneous and endothermic in nature. The adsorption activation energy (E_a) for CR (124 kJ mol^?1) implied chemical adsorption while that for BV (5.4 kJ mol^?1) indicated physical adsorption. An increase in the Thomas model constant (K_Th) with increasing flow indicated that for both dyes the mass transport resistance decreased during adsorption. Thus, CPS may be an efficient low-cost adsorbent for decolorization of dye-containing wastewaters.     

Removal of Mo(VI) from aqueous solutions using sulfuric acid-modified cinder: kinetic and thermodynamic studies

Removal of Mo(VI) from aqueous solutions was investigated using cinder modified by sulfuric acid. Various parameters such as pH, agitation time, Mo(VI) concentration, and temperature have been studied. The maximum adsorption of Mo(VI) occurred at pH between 4.0 and 6.0. Kinetic studies showed that the adsorption generally obeyed a pseudo second-order model. The activation energy was 31.4?kJ?mol^?1, indicating that the adsorption process was governed mainly by interactions of physical nature. Furthermore, application of Langmuir and Freundlich isotherm models to the adsorption equilibrium data showed that the adsorption behavior obeyed the Langmuir model. The adsorption capacity was found to be 10.8?g Mo(VI)?kg^?1 adsorbent. Finally, thermodynamic parameters such as ΔH ⁰, ΔS ⁰, and ΔG ⁰ were also evaluated, which showed that the adsorption of Mo(VI) on the treated cinder was endothermic, entropy increasing, and spontaneous. In conclusion, the sulfuric acid-modified cinder was shown to be an inexpensive, effective, and simple adsorbent for the removal of Mo(VI) from water.     

干旱区绿洲灌漠土Cu、Zn和Pb的吸附解吸特征

土壤重金属吸附解吸是影响土壤系统中重金属移动性和归宿的主要过程,影响重金属的生物有效性以及重金属在食物链中的传递等.配制一系列不同浓度的重金属,灌漠土对重金属溶液进行吸附实验24 h以达到平衡,再用硝酸铵和乙酸铵进行解吸实验24 h以达到平衡.利用热力学吸附平衡法,对西北干旱区绿洲灌漠土重金属Cu、Ni和Pb的吸附解吸行为进行序批实验研究.实验结果表明:(1)灰漠土在常温下对铜、锌和铅重金属离子的吸附等温线符合Freundlich型吸附模式,灰漠土对重金属铜、锌和铅的吸附能力由强到弱的顺序为:铅,铜,锌.(2)硝酸铵和乙酸铵解吸重金属的量与灰漠土吸附重金属量呈现出线性正相关,乙酸铵解吸重金属的量比硝酸铵解吸重金属的量大,两种解吸剂对铜、锌和铅重金属离子的解吸能力由大到小的顺序都为:铜,锌,铅,说明了一般外源的铜、锌和铅进入土壤以后,铜和锌可能比铅容易向四周转移.(3)硝酸铵和乙酸铵的解吸率呈谷形曲线,开始时硝酸铵和乙酸铵解吸重金属量的百分比随灰漠土吸附重金属量的增加而减小,在吸附量达到某一特定值时,解吸率随吸附量的增加而增加.灰漠土对铜、锌和铅的吸附作用以专性吸附为主,被灰漠土吸附的铜、锌和铅重金属离子较难解吸.     

Biosorption of Cr(III) from aqueous solution by freeze-dried activated sludge: Equilibrium,kinetic and thermodynamic studies

Batch biosorption experiments were conducted to remove Cr(III) from aqueous solutions using activated sludge from a sewage treatment plant. An investigation was conducted on the effects of the initial pH, contact time, temperature, and initial Cr(III) concentration in the biosorption process. The results revealed that the activated sludge exhibited the highest Cr(III) uptake capacity (120 mg·g⁻¹) at 45°C, initial pH of 4, and initial Cr(III) concentration of 100 mg·L⁻¹. The biosorption results obtained at various temperatures showed that the biosorption pattern accurately followed the Langmuir model. The calculated thermodynamic parameters, ΔG^o (−0.8– −4.58 kJ·mol⁻¹), ΔH^o (15.6–44.4 kJ·mol⁻¹), and ΔS^o (0.06–0.15 kJ·mol⁻¹·K⁻¹) clearly indicated that the biosorption process was feasible, spontaneous, endothermic, and physical. The pseudo first-order and second-order kinetic models were adopted to describe the experimental data, which revealed that the Cr(III) biosorption process conformed to the second-order rate expression and the biosorption rate constants decreased with increasing Cr(III) concentration. The analysis of the values of biosorption activation energy (E_a = −7 kJ·mol⁻¹) and the intra-particle diffusion model demonstrated that Cr(III) biosorption was film-diffusion-controlled.     

Crosslinking acrylamide with EDTA-intercalated layered double hydroxide for enhanced recovery of Cr(VI) and Congo red: Adsorptive and mechanistic study

• Functional groups of AM and EDTA in composite increased removal of Cr(VI) and CR. • Removal process reached equilibrium within 30 min and was minimally affected by pH. • Elimination of Cr(VI) was promoted by coexisting CR. • Adsorption process of CR was less influenced by the presence of Cr(VI). • Mechanisms were electrostatic attraction, surface complexation and anion exchange. We prepared ethylenediaminetetraacetic acid (EDTA)-intercalated MgAl-layered double hydroxide (LDH-EDTA), then grafted acrylamide (AM) to the LDH-EDTA by a cross-linking method to yield a LDH-EDTA-AM composite; we then evaluated its adsorptive ability for Congo red (CR) and hexavalent chromium (Cr(VI)) in single and binary adsorption systems. The adsorption process on LDH-EDTA-AM for CR and Cr(VI) achieved equilibrium quickly, and the removal efficiencies were minimally affected by initial pH. The maximum uptake quantities of CR and Cr(VI) on LDH-EDTA-AM were 632.9 and 48.47 mg/g, respectively. In mixed systems, chromate removal was stimulated by the presence of CR, while the adsorption efficiency of CR was almost not influenced by coexisting Cr(VI). The mechanisms involved electrostatic attraction, surface complexation, and anion exchange for the adsorption of both hazardous pollutants. In the Cr(VI) adsorption process, reduction also took place. The removal efficiencies in real contaminated water were all higher than those in the laboratory solutions.     

Sorption of cadmium(II) and copper(II) by soil humic acids: temperature effects and sorption heterogeneity

Sorption by humic acids is known to modify the bioavailability and toxicity of metals in soils and aquatic systems. The sorption of cadmium(II) and copper(II) to two soil humic acids was measured at pH 6.0 using ion-selective electrode potentiometric titration at different temperatures. Sorption reactions were studied with all components in aqueous solution, or with the humates in suspension. Adsorption reactions were described using a multiple site-binding model, and a model assuming a continuous log-normal distribution of adsorption constants. Adsorption of Cu²⁺ was more favourable than adsorption of Cd²⁺. The log-normal distribution model provided the closest fit to observations and allowed parameterisation of adsorption data using a mean adsorption constant (log K _μ). Sorption of Cd²⁺ to dissolved humic acids increased slightly in extent and sorption affinity with increasing temperature, but the effect was small (log K _μ 2.96–3.15). A slightly greater temperature effect occurred for sorption of Cd²⁺ to solid-phase humic acids (log K _μ 1.30–2.08). Sorption of copper(II) to both aqueous- and colloidal-phase humates showed more pronounced temperature dependence, with extent of sorption, and sorption affinity, increasing with increasing temperature (log K _μ 3.4–4.9 in solution and 1.4–4.5 in suspension). The weaker adsorption of Cd²⁺ than Cu²⁺, and smaller temperature effects for dissolved humates than suspended humates, suggested that the observed temperature effects had a kinetic, rather than thermodynamic, origin. For any metal-to-ligand ratio, free metal ion concentration, and by inference metal bioavailability, decreased with increasing temperature. The consistency of the data with kinetic rather than thermodynamic control of metal bioavailability suggests that equilibrium modelling approaches to estimating bioavailability may be insufficient.