Enhanced dechlorination of 2,4-dichlorophenol by recoverable Ni/Fe–Fe3O4 nanocomposites

Ni/Fe-Fe_3O_4 nanocomposites were synthesized for dechlorination of 2,4-dichlorophenol(2,4-DCP). The effects of the Ni content in Ni/Fe-Fe_3O_4 nanocomposites, solution pH, and common dissolved ions on the dechlorination efficiency were investigated, in addition to the reusability of the nanocomposites. The results showed that increasing content of Ni in Ni/Fe–Fe_3O_4 nanocomposites, from 1 to 5 wt.%, greatly increased the dechlorination efficiency; the Ni/Fe–Fe_3O_4 nanocomposites had much higher dechlorination efficiency than bare Ni/Fe nanoparticles. Ni content of 5 wt.% and initial p H below 6.0 was found to be the optimal conditions for the catalytic dechlorination of 2,4-DCP. Both 2,4-DCP and the intermediate product 2-chlorophenol(2-CP) were completely removed, and the concentration of the final product phenol was close to the theoretical phenol production from complete dechlorination of 20 mg/L of 2,4-DCP, after 3 hr reaction at initial p H value of 6.0,3 g/L Ni/Fe-Fe_3O_4 , 5 wt.% Ni content in the composite, and temperature of 22℃. 2,4-DCP dechlorination was enhanced by Cl-and inhibited by NO3-and SO_4~(2-). The nanocomposites were easily separated from the solution by an applied magnetic field. When the catalyst was reused, the removal efficiency of 2,4-DCP was almost 100% for the first seven uses, and gradually decreased to 75% in cycles 8–10. Therefore, the Ni/Fe–Fe_3O_4 nanocomposites can be considered as a potentially effective tool for remediation of pollution by 2,4-DCP.     

柠檬酸-沼气双发酵耦联工艺中钠离子的影响

提出了柠檬酸-沼气双发酵耦联工艺,用于处理柠檬酸发酵过程中产生的废水,柠檬酸废水经厌氧消化处理后作为配料水回用于下一批次的柠檬酸发酵,从而实现废水零排放。厌氧水中超过1 000mg/L的Na~+在回用过程中会严重抑制柠檬酸发酵,柠檬酸产量为118.5 g/L,较空白下降了15.6%。单因素试验表明,Na~+对柠檬酸发酵的抑制质量浓度为200 mg/L。通过对发酵过程中糖化酶、异麦芽糖酶及柠檬酸合成酶、异柠檬酸脱氢酶等胞内关键酶活力变化的分析,初步探讨了其影响机理。结果表明,高达1 000 mg/L的Na~+会导致黑曲霉胞内异柠檬酸脱氢酶活力升高,柠檬酸代谢活力增强。同时,培养基中糖化酶和异麦芽糖酶活力受到抑制,发酵结束时部分糊精和异麦芽糖不能被完全降解,残总糖质量浓度升高至30 g/L,黑曲霉可利用的糖浓度减小,柠檬酸合成速率和柠檬酸产量降低。加入过量糖化酶可以有效减弱高质量浓度Na~+的抑制作用,但柠檬酸产量仍然低于去离子水发酵。     

北京灰霾天PM_(2.5)中有机官能团和无机离子的ATR-FTIR研究

采用傅里叶变换衰减全反射红外光谱法(ATR-FTIR)研究北京西北城区灰霾天气下PM_(2.5)中有机官能团(R-OH羟基、R-CH脂肪族碳氢基、R-CO-羰基、R-NO2硝基官能团)和无机离子(NH_4~+、SO_4~(2-)、NO_3~-)的变化规律.结果表明,PM_(2.5)中无机离子(NH_4~+、SO_4~(2-)、NO_3~-)的ATR-FTIR吸收峰值高于有机官能团(R-CH,R-CO-,R-NO_2,R-OH)的峰值;有机官能团R-CH的吸收峰峰值高于R-CO-和R-NO_2官能团的吸收峰,R-OH官能团的吸收峰峰值最低.灰霾天PM_(2.5)中各有机官能团和无机离子的ATR-FTIR吸收峰值明显高于非灰霾天.说明灰霾天气下PM_(2.5)中这些官能团及无机离子的质量浓度均高于非灰霾天.灰霾天PM_(2.5)中无机离子(NH_4~+、SO_4~(2-)、NO_3~-)质量浓度高于有机官能团(R-CH,R-CO-,R-NO_2,R-OH)的质量浓度,且有机官能团以R-CH为主,R-CO-,R-NO_2次之,R-OH最少.     

石家庄夏季大气PM_(10)和水溶性离子污染特征

于2014年7月在石家庄市区对大气环境PM_(10)进行样品采集,并对PM_(10)浓度和水溶性离子的污染特征进行了分析。结果表明:采样期间PM_(10)质量浓度为(145.2±58.7)μg/m3,重污染天气主要是由于气象条件和地理位置共同造成的。水溶性离子是PM_(10)中含量较高的组分,其中SO2-4、NO-3和NH+4之和占总水溶性离子质量浓度的80.7%,Ca2+和Mg2+相关系数高达0.88,表明两者来源一致,Na+和Cl-浓度受人为活动的影响较大,K+主要来自生物质燃烧。PM_(10)中硫氧化率和氮氧化率分别为0.37和0.28,表明大气中存在SO2和NO2二次转化过程。     

Evaluation of carbon-based nanosorbents synthesised by ethylene decomposition on stainless steel substrates as potential sequestrating materials for nickel ions in aqueous solution

The present work covers the preparation of carbon-based nanosorbents by ethylene decomposition on stainless steel mesh without the use of external catalyst for the treatment of water containing nickel ions (Ni²⁺). The reaction temperature was varied from 650 to 850℃, while reaction time and ethylene to nitrogen flow ratio were maintained at 30 min and 1:1 cm³/min, respectively. Results show that nanosorbents synthesised at a reaction temperature of 650℃ had the smallest average diameter (75 nm), largest BET surface area (68.95 m²/g) and least amount of impurity (0.98 wt.% Fe). A series of batch sorption tests were performed to evaluate the effects of initial pH, initial metal concentration and contact time on Ni²⁺ removal by the nanosorbents. The equilibrium data fitted well to Freundlich isotherm. The kinetic data were best correlated to a pseudo second-order model indicating that the process was of chemisorption type. Further analysis by the Boyd kinetic model revealed that boundary layer diffusion was the controlling step. This primary study suggests that the prepared material with Freundlich constants compared well with those in the literature, is a promising sorbent for the sequestration of Ni²⁺ in aqueous solutions.     

Chemical compositions of PM2.5 aerosol during haze periods in the mountainous city of Yong'an, China

Haze phenomena were found to have an increasing tendency in recent years in Yong'an, a mountainous industrial city located in the center part of Fujian Province, China. Atmospheric fine particles (PM_2.5) in the urban area during haze periods in three seasons (spring, autumn and winter) from 2007 to 2008 were collected, and the mass concentrations and chemical compositions (seventeen elements, water soluble inorganic ions (WSIIs) and carbonaceous species) of PM_2.5 were determined. PM_2.5 mass concentrations did not show a distinct difference among the three seasons. The carbonaceous species organic carbon (OC) and elemental carbon (EC) constituted up to 19.2%-30.4% of the PM_2.5 mass during sampling periods, while WSIIs made up 25.3%-52.5% of the PM_2.5 mass. The major ions in PM_2.5 were SO₄^2-, NO₃^- and NH₄⁺, while the major elements were Si, K, Pb, Zn, Ca and Al. The experimental results (from data based on three haze periods with a 10-day sampling length for each period) showed that the crustal element species was the most abundant component of PM_2.5 in spring, and the secondary ions species (SO₄^2-, NO₃^-, NH₄⁺, etc.) was the most abundant component in PM_2.5 in autumn and winter. This indicated that dust was the primary pollution source for PM_2.5 in spring and combustion and traffic emissions could be the main pollution sources for PM_2.5 in autumn and winter. Generally, coal combustion and traffic emissions were considered to be the most prominent pollution sources for this city on haze days.     

Adsorptive removal of iron and manganese ions from aqueous solutions with microporous chitosan/polyethylene glycol blend membrane

Microporous chitosan (CS) membranes were directly prepared by extraction of poly(ethylene glycol) (PEG) from CS/PEG blend membrane and were examined for iron and manganese ions removal from aqueous solutions. The different variables affecting the adsorption capacity of the membranes such as contact time, pH of the sorption medium, and initial metal ion concentration in the feed solution were investigated on a batch adsorption basis. The affinity of CS/PEG blend membrane to adsorb Fe(II) ions is higher than that of Mn(II) ions, with adsorption equilibrium achieved after 60 min for Fe(II) and Mn(II) ions. By increasing CS/PEG ratio in the blend membrane the adsorption capacity of metal ions increased. Among all parameters, pH has the most significant effect on the adsorption capacity, particularly in the range of 2.9-5.9. The increase in CS/PEG ratio was found to enhance the adsorption capacity of the membranes. The effects of initial concentration of metal ions on the extent of metal ions removal were investigated in detail. The experimental data were better fitted to Freundlich equation than Langmuir. In addition, it was found that the iron and manganese ions adsorbed on the membranes can be effectively desorbed in 0.1 mol/L HCl solution (up to 98% desorption efficiency) and the blend membranes can be reused almost without loss of the adsorption capacity for iron and manganese ions.     

碳基吸附剂原位吸附底泥重金属离子研究进展

本文综述了碳基吸附剂去除湖泊底泥中重金属离子的研究进展,具体介绍了生物炭基吸附剂、碳纳米管基吸附剂以及氧化石墨烯基吸附剂在修复湖泊重金属污染底泥中的应用,分析了影响重金属污染底泥修复的影响因素.结果表明,生物炭基吸附剂,碳纳米管基吸附剂,氧化石墨烯基吸附剂以及改性碳基吸附剂均能够有效修复底泥重金属,抑制重金属的生物有效性,同时上覆水pH值、氧化还原电位、有机质和水体扰动会影响重金属修复效果.最后针对碳基吸附剂在修复底泥重金属方面的局限性,展望了未来碳基吸附剂修复湖泊重金属污染底泥的发展方向.     

Intensified wintertime secondary inorganic aerosol formation during heavy haze pollution episodes (HPEs) in Beijing, China

Air pollution in China is complex, and the formation mechanism of chemical components in particulate matter is still unclear. This study selected three consecutive heavy haze pollution episodes (HPEs) during winter in Beijing for continuous field observation, including an episode with heavy air pollution under red alert. Clean days during the observation period were selected for comparison. The HPE characteristics of Beijing in winter were: under the influence of adverse meteorological conditions such as high relative humidity, temperature inversion and low wind speed; and strengthening of secondary transformation reactions, which further intensified the accumulation of secondary aerosols and other pollutants, promoting the explosive growth of PM_2.5. PM_2.5/CO values, as indicators of the contribution of secondary transformation in PM_2.5, were approximately 2 times higher in the HPEs than the average PM_2.5/CO during the clean period. The secondary inorganic aerosols (sulfate nitrate and ammonium salt) were significantly enhanced during the HPEs, and the conversion coefficients were remarkably improved. In addition, it is interesting to observe that the production of sulfate tended to exceed that of nitrate in the late stage of all three HPEs. The existence of aqueous phase reactions led to the explosive growth sulfur oxidation ratio (SOR) and rapid generation of sulfate under high relative humidity (RH>70%).     

Surface protection method for the magnetic core using covalent organic framework shells and its application in As(III) depth removal from acid wastewater

Fe₃O₄-based materials are widely used for magnetic separation from wastewater. However, they often suffer from Fe-leaching behavior under acidic conditions, decreasing their activity and limiting sustainable practical applications. In this study, covalent organic frameworks (COFs) were used as the shell to protect the Fe₃O₄ core, and the Fe₃O₄@COF core-shell composites were synthesized for As(III) removal from acid wastewater. The imine-linked COFs can in situ grow on the surface of the Fe₃O₄ core layer by layer with [COFs/Fe₃O₄]_mol ratio of up to 2:1. The Fe-leaching behavior was weakened over a wide pH range of 1-13. Moreover, such composites keep their magnetic characteristic, making them favorable for nanomaterial separation. As(III) batch adsorption experiments results indicated that, when COFs are used as the shell for the Fe₃O₄ core, a balance between As(III) removal efficiencies and the thickness of the COF shell exists. Higher As(III) removal efficiencies are obtained when the [COFs/Fe₃O₄]_mol ratios were < 1.5:1, but thicker COF shells were not beneficial for As(III) removal. Such composites also exhibited better As(III) removal performances in the pH range of 1–7. Over a wide pH range, the zeta potential of Fe₃O₄@COF core-shell composites becomes more positive, which benefits the capture of negative arsenic ions. In addition, thinner surface COFs were favorable for mass transfer and facilitating the reaction of Fe and As elements. Our study highlights the promise of using COFs in nanomaterial surface protection and achieving As(III) depth removal under acidic conditions.