Synthesis of nitrogen-doped carbon nanotubes-FePO4 composite from phosphate residue and its application as effective Fenton-like catalyst for dye degradation

Phosphate residue is regarded as a hazardous waste, which could potentially create significant environmental and health problems if it is not properly treated and disposed of. In this study, nitrogen-doped carbon nanotubes-FePO_4(NCNTs-FePO_4) composite was successfully synthesized from phosphate residue, and its application as an effective catalyst was explored. Firstly, an effective method was developed to recover FePO_4 from phosphate residue, achieving an impressive FePO_4 mass recovery rate of 98.14%. Then, the NCNTsFePO_4 catalyst was synthesized from the recovered FePO_4 by two main reactions, including surface modification and chemical vapor deposition. Finally, the synthesized NCNTs-FePO_4 was applied to photo-degrade 15 mg/L Rhodamine B(RhB) in a Fenton-like system. The results showed that 98.9% of RhB could be degraded in 60 min, closely following the pseudofirst-order kinetics model. It was found that even after six consecutive cycles, NCNTs-FePO_4 still retained a high catalytic capacity(50%). Moreover, ·OH radicals participating in the RhB degradation process were evidenced using quenching experiments and electron paramagnetic resonance analysis, and a rational mechanism was proposed. It was demonstrated that the materials synthesized from hazardous phosphate residue can be used as an effective catalyst for dye removal.     

Rapid removal of polyacrylamide from wastewater by plasma in the gas–liquid interface

Due to the severe restrictions imposed by legislative frameworks, the removal of polyacrylamide(PAM) rapidly and effectively from produced wastewater in offshore oilfields before discharge is becoming an urgent challenge. In this study, a novel advanced oxidation process based on plasma operated in the gas–liquid interface was used to rapidly decompose PAM, and multiple methods including viscometry, flow field-flow fractionation multi-angle light scattering, UV–visible spectroscopy, and attenuated total reflectanceFourier transform infrared spectroscopy were used to characterize the changes of PAM.Under a discharge voltage of 25 kV and pH 7.0, the PAM concentration decreased from 100 to 0 mg/L within 20 min and the total organic carbon(TOC) decreased from 49.57 to1.23 mg/L within 240 min, following zero-order reaction kinetics. Even in the presence of background TOC as high as 152.2 mg/L, complete removal of PAM(100 mg/L) was also achieved within 30 min. The biodegradability of PAM improved following plasma treatment for 120 min. Active species(such as O_3 and H_2O_2) were produced in the plasma. Hydroxyl radical was demonstrated to play an important role in the degradation of PAM due to the inhibitory effect observed after the addition of an ·OH scavenger, Na_2CO_3. Meanwhile, the release of ammonia and nitrate nitrogen confirmed the cleavage of the acylamino group.The results of this study demonstrated that plasma, with its high efficiency and chemicalfree features, is a promising technology for the rapid removal of PAM.     

Potential factors and mechanism of particulate matters explosive increase induced by free radicals oxidation

Atmospheric particulate pollution in China has attracted much public attention. Occasionally, the particle number concentration increases sharply in a short time period, which is defined as a “particulate matter explosive increase”. Heavy particulate matter pollution not only reduces visibility but also has an adverse effect on human health. Hence, there is an urgent need to discover the causes of particulate matter explosive increase. During this campaign, the particle number concentration and free radicals were measured at a tall building on the campus of Lanzhou University of Technology. Additionally, we examined a series of chemicals to reproduce the observed particulate matter explosive increase in a smog chamber to determine its potential factors. Then, we analyzed the mechanism of particulate matter explosive increase in the presence of free radicals. We found that, among the potential inorganic and organic sources analyzed, a mixture of organic and SO₂ in the research region had a major effect on particulate matter explosive increase. Moreover, free radical oxidation has a large effect, especially in the formation of organic particulates.     

菹草和伊乐藻对水-沉积物界面磷迁移转化的影响

冬季沉水植物普遍凋亡,死亡残体易造成湖泊二次污染.为探究冬季耐寒性沉水植物对水-沉积物界面各形态磷迁移转化的影响,选取根系特征不同的冬季耐寒性沉水植物菹草（Potamogeton crispus L.）和伊乐藻（Elodea nuttallii）作为研究对象,测定其冬季生长期间上覆水、间隙水和沉积物中各形态磷的含量,并监测环境因子的变化.结果表明:①菹草、伊乐藻组生长期间水-沉积物界面各形态磷含量总体呈下降趋势,并在一定时期维持较低水平,菹草对沉积物和间隙水磷的吸收效果优于伊乐藻,而伊乐藻对上覆水磷的影响大于菹草.②试验第30天后,菹草、伊乐藻组上覆水和间隙水各形态磷质量浓度均显著低于对照组（P < 0.05）,上覆水中ρ（TP）最低值分别为0.057和0.041 mg/L,间隙水中ρ（DTP）（DTP表示溶解性总磷）分别维持在0.270~0.505、0.384~0.507 mg/L之间.③试验结束时,菹草组沉积物中w（TP）、w（IP）（IP表示无机磷）和w（NaOH-P）（NaOH-P表示NaOH提取态磷）分别低至643.68、415.79和120.17 mg/kg,分别下降了16.54%、18.37%和35.82%,伊乐藻组分别低至700.39、457.87和145.29 mg/kg,分别下降了10.24%、11.17%和24.67%;菹草、伊乐藻植株体内TP质量分别增加了588.94和464.59 mg.研究显示,菹草、伊乐藻在生长期间均能有效吸收磷,同时改变了pH、E_h等环境因子,从而影响磷在水-沉积物界面的迁移及磷形态的转变.      

磁性氮掺杂碳材料活化过硫酸盐降解酸性橙7

采用一步水热碳化法制备出微米级磁性氮掺杂碳材料（Magnetic N-doped Carbonaceous Materials,MNC）作为过硫酸盐（Persulfate,PDS）活化剂,以生成的活性氧化物质降解偶氮类染料酸性橙7（Acid Orange 7,AO7）.同时,利用扫描电镜（SEM）、比表面积与孔径测定仪（BET）、振动样品磁强计（VSM）等对MNC进行表征,考察了MNC投加量、PDS浓度、初始p H值和无机阴离子对活化PDS降解AO7的影响,并采用紫外-可见光谱分析、淬灭实验和电子顺磁性共振（Electron Paramagnetic Resonance,EPR）初步探讨了AO7的降解机理.结果表明,MNC呈微米级球状,表面富含含氧基团和氨基等活性点位;饱和磁化强度为12.7 emu·g^-1,能在外加磁场条件下实现固液分离.AO7去除率随MNC投加量、PDS浓度的增加而增加,但初始p H对AO7降解的影响呈相反规律,随p H升高而降低.3种无机阴离子对AO7降解抑制程度大小顺序为HCO₃^->SO     

Anthraquinone acted as a catalyst for the removal of triphenylmethane dye containing tertiary amino group: Characteristics and mechanism

Herein, we found that anthraquinone (AQ) acted as a catalyst for the rapid and effective removal of triphenylmethane dye containing tertiary amino group (TDAG). Results showed that AQ had an enhanced catalytic reactivity towards the removal of TDAG compared to hydro-quinone, which was further proved and explained using density functional theory (DFT) calculations. AQs could achieve a TDAG removal efficiency and rate of approximately 100% and 0.3583 min⁻¹, respectively, within 20 min. Quenching experiments and electron paramagnetic resonance (EPR) tests indicated that the superoxide radical (O₂^•−) generated through the catalytic reduction of an oxygen molecule (O₂) by AQ contributed to the effective removal of the TDAG. In addition, it was found that the electrophilic attack of the O₂^•− radical on the TDAG was the driving force for the dye degradation process. Decreasing the pH led to protonation of the substituted group of AG, which resulted in formation of an electron deficient center in the TDAG molecule (TDAG-EDC⁺) through delocalization of the π electron. Therefore, the possibility of the electrophilic attack for the dye by the negative O₂^•- radical was significantly enhanced. This study revealed that the H⁺ and the O₂^•− generated by the catalytic reduction of O₂ have synergistic effects that led to a significant increase in the dye removal rate and efficiency, which were higher than those obtained through persulfate oxidation.     

FeS-Fe0纳米复合材料活化过硫酸盐降解双酚S的研究

双酚S(BPS)是一种新兴的内分泌干扰物,在环境中广泛存在,并对自然环境和人体健康有严重危害。制备了FeS-Fe⁰纳米复合材料作为催化剂,明确了FeS-Fe⁰纳米复合材料活化PS体系(FeS-Fe⁰/PS体系)的反应条件对去除BPS的影响,包括材料中FeS与Fe⁰摩尔比、材料投加量、PS浓度、溶液初始pH值等,并应用X射线衍射分析、X射线光电子能谱分析等技术表征该复合材料,通过反应体系对比实验、Fe离子溶出实验、PS的消耗实验、猝灭实验、电子顺磁共振波谱检测,探究了FeS-Fe⁰纳米复合材料的活化机理。实验结果表明:FeS-Fe⁰/PS体系降解BPS的最优条件为溶液初始pH=3、FeS与Fe⁰摩尔比1∶25、材料投加量0.10 g/L、PS浓度1.0 mM;FeS-Fe⁰/PS体系中产生的硫酸根自由基(SO₄^·-)和羟基自由基(HO·)可降解BPS,且HO·占主导作用;FeS-Fe⁰纳米复合材料表面的FeS促进了铁离子的溶出和循环,因此其活化能力优于纳米零价铁。     

不同氨氮填加量下沉水植物对沉积物DOM荧光特性的影响

采用三维荧光光谱技术,模拟研究了不同氨氮添加量(0,100,200和400 mg/kg)下沉水植物对湖泊沉积物DOM(溶解性有机质)荧光特性的影响.结果表明:不同氨氮添加量下,沉水植物的存在明显增强沉积物DOM荧光强度,其中对类蛋白质和类氨基酸组分荧光强度影响较大(荧光强度分别增大了20%～77%和27%～56%);而对类腐殖酸和类富里酸组分影响相对较小(荧光强度分别增大了5%～25%和21%～29%). 添加氨氮可增强沉水植物对沉积物DOM荧光强度影响的程度,当添加量为100 mg/kg时,沉水植物生长最旺盛,沉积物DOM中类蛋白质和类氨基酸组分荧光强度增幅最大(分别约77%和56%);即外源氨氮通过增加沉积物蛋白质和氨基酸含量增强了沉积物有机氮的生物有效性;而在其他添加量下,DOM各荧光组分强度增幅不大,即适当添加外源氨氮,可通过促进沉水植物生长增加沉积物中蛋白质和氨基酸等含量,从而提高沉积物有机氮的生物有效性.      

不同特性底质对沉水植物恢复生长的影响

通过室内模拟实验,研究了3种土壤基质（沙土、粘土和腐殖土）分别与河岸边土壤按5个质量分数（5%、10%、30%、50%和80%）掺混形成的不同成分底质分别对菹草（Potamogeton crispus）、轮叶黑藻（Hydrilla verticillata）和微齿眼子菜（Potamogeton maackianus）顶枝断枝恢复生长的影响。结果表明：（1）在3种基质与岸边土壤掺混的底质上,实验结束时菹草的平均最高植株分别出现在5%SA（沙土与岸边土掺混）底质、50%NA（粘土与岸边土掺混）底质和10%FA（腐殖土与岸边土掺混）底质,株高分别达到30、48和45 cm;轮叶黑藻的平均最高植株分别出现在10%SA底质、50%NA底质和30%FA底质,株高分别达到47、82和59 cm;微齿眼子菜在3种基质掺混的底质上植株株高几乎没有增高;（2）生长于同种底质的植株,单位高度上菹草的生物量大于轮叶黑藻,微齿眼子菜的生物量几乎没有增加。因此,适宜菹草和轮叶黑藻恢复生长的基质顺序为粘土〉腐殖土〉沙土,微齿眼子菜在3种基质掺混的底质上几乎没有生长;植株对于特性底质适应性强弱的顺序依次为轮叶黑藻〉菹草〉微齿眼子菜。     

不同浓度铵态氮对苦草的生理影响

研究了苦草在不同浓度(0.02,0.05,0.10,0.30,0.60,1.00,3.00mg/L)铵态氮中暴露14d后,其生物量的变化、叶片游离氨基酸态氮、叶绿素、可溶性蛋白含量以及O2-×信号强度、抗氧化酶活性和丙二醛(MDA)含量的响应.结果表明,各浓度组苦草的生物量无显著变化,但是各生理指标变化显著.当铵态氮浓度为0.30mg/L时,苦草叶片中游离氨基酸态氮的含量即开始显著升高.当铵态氮浓度达到0.60mg/L时,超氧化物歧化酶(SOD)活性显著升高,表明苦草诱导产生氧化应激但未受到氧化损伤.当铵态氮浓度高于1.00mg/L时,SOD和过氧化物酶(POD)活性显著升高,O2-×信号强度显著增强,叶绿素、可溶性蛋白含量显著降低.当铵态氮浓度为0.02mg/L时,O2-×信号强度显著增强.综上,铵态氮浓度低于0.60mg/L苦草生长良好,浓度31.00mg/L苦草光合能力受到抑制、代谢受到干扰.苦草对铵态氮最敏感的生理生化指标是叶片中游离氨基酸态氮含量.铵态氮作为沉水植物的一种营养物质,当其含量较低时,植物由于营养缺乏诱导产生自由基.