Stability of 6:2 fluorotelomer sulfonate in advanced oxidation processes: degradation kinetics and pathway

Perfluorooctane sulfonate (PFOS), a widely used mist suppressant in hard chrome electroplating industry, has been listed in the Stockholm Convention for global ban. 6:2 Fluorotelomer sulfonate (6:2 FTS) acid and salts have been adopted as alternative products in the market, but no data about their abiotic degradation has been reported. In the present study, the degradability of 6:2 FTS potassium salt (6:2 FTS-K) was evaluated under various advanced oxidation processes, including ultraviolet (UV) irradiation, UV with hydrogen peroxide (H₂O₂), alkaline ozonation (O₃, pH = 11), peroxone (O₃/H₂O₂), and Fenton reagent oxidation (Fe²⁺/H₂O₂). UV/H₂O₂ was found to be the most effective approach, where the degradation of 6:2 FTS-K followed the pseudo-first-order kinetics. The intermediates were mainly shorter chain perfluoroalkyl carboxylic acid (C₇ to C₂), while sulfate (SO₄ ^2?) and fluoride (F^?) were found to be the final products. The high yields of SO₄ ^2? and F^? indicate that 6:2 FTS-K can be nearly completely desulfonated and defluorinated under UV/H₂O₂ condition. The degradation should firstly begin with the substitution of hydrogen atom by hydroxyl radicals, followed by desulfonation, carboxylation, and sequential “flake off” of CF₂ unit. Compared with PFOS which is inert in most advanced oxidation processes, 6:2 FTS-K is more degradable as the alternative.     

新型硅镁胶(MgO·2SiO_2)对模拟放射性废水中Co~(2+)的吸附性能

以泡花碱和氯化镁为原料合成出了一种新型硅镁胶(MgO·2SiO2)吸附材料,用傅里叶红外光谱仪对其进行了表征,并对模拟放射性废水中的Co2+进行吸附实验。结果表明,控制合成pH在10.50~11.00,可以得到目标硅镁胶(MgO·2SiO2),在460 cm-1处出现了较强的吸收峰,这是由Mg—O伸缩振动和Si—Mg—O弯曲振动引起。在500℃焙烧4h后,可以得到吸附性能良好的硅镁胶,随着溶液pH的升高,去除率增大,在pH为4~8时达到最大。25℃时,最大吸附量可达135.5 mg/g,吸附过程符合Langmuir等温吸附方程和准二级动力学方程。重复使用4次,对Co2+的吸附量仍然达到130 mg/g,说明硅镁胶是一种可重复利用的吸附剂。     

Ag/ZnO hollow sphere composites: reusable photocatalyst for photocatalytic degradation of 17α-ethinylestradiol

Characterizations of Ag/ZnO hollow sphere by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectra, and UV–vis absorption spectra have been made after its synthesis. The results showed that the composite was hollow structure with diameters of about 1–4 μm. The samples synthesized were tested and identified as silver doped ZnO, which have extended and boosted the spectral absorption. The photocatalytic activity of Ag/ZnO hollow spheres was assessed using 17α-ethinylestradiol aqueous solution under UV irradiation. It has been observed that the 17α-ethinylestradiol absorption efficiency and degradation rate is higher for Ag/ZnO hollow spheres. As reusable photocatalysts, Ag/ZnO hollow spheres which could be easily separated from a suspension will facilitate their application in wastewater treatment with enhanced photostability.     

Quantifying interactions between propranolol and dissolved organic matter (DOM) from different sources using fluorescence spectroscopy

Beta blockers are widely used pharmaceuticals that have been detected in the environment. Interactions between beta blockers and dissolved organic matter (DOM) may mutually alter their environmental behaviors. To assess this potential, propranolol (PRO) was used as a model beta blocker to quantify the complexation with DOM from different sources using the fluorescence quenching titration method. The sources of studied DOM samples were identified by excitation–emission matrix spectroscopy (EEMs) combined with fluorescence regional integration analysis. The results show that PRO intrinsic fluorescence was statically quenched by DOM addition. The resulting binding constants (log K _oc) ranged from 3.90 to 5.20, with the surface-water-filtered DOM samples claiming the lower log K _oc and HA having the highest log K _oc. Log K _oc is negatively correlated with the fluorescence index, biological index, and the percent fluorescence response (P _i,n) of protein-like region (P _I,n) and the P _i,n of microbial byproduct-like region (P _II,n) of DOM EEMs, while it is correlated positively with humification index and the P _i,n of UVC humic-like region (P _III,n). These results indicate that DOM samples from allochthonous materials rich in aromatic and humic-like components would strongly bind PRO in aquatic systems, and autochthonous DOM containing high protein-like components would bind PRO more weakly.     

溴酸钾对二茂铁(Fc)非均相Fenton效能的影响

研究了KBrO3对二茂铁(Fc)非均相Fenton效能的影响,深入考察了KBrO3对体系中Fc溶解、H2O2分解和羟基自由基(·OH)生成的影响。结果表明,KBrO3的加入对不同反应阶段Fc/Fenton体系的效能均有明显的促进作用,初始阶段主要是由于KBrO3对·OH产生的促进作用所致,后期主要是由于KBrO3促进了体系中Fc的溶解,使得体系中溶解态的Fc催化的均相Fenton反应的比例增加,体系中H2O2的分解加快,·OH的表观生成率增加,进而促进了反应的进行。无KBrO3添加,pH=4,MB初始浓度为10 mg/L,Fc的量为1.6×10-3mol/L,[H2O2]/[MB]=3.14时,45 min时,MB的剩余率为9.1%,105 min时为0。当KBrO3的用量为3×10-4mol/L时,反应45 min后MB的去除率即可达到100%。随着KBrO3浓度的增加,其对Fc/Fenton效能的促进作用增强。     

水平潜流人工湿地在不同水力负荷下的水力效率及可视化分析

构建水平潜流人工湿地装置,通过NaCl示踪脉冲实验,得到不同水力负荷条件下的水力停留时间分布密度曲线,根据不同停留时间的关系计算相对水力效率,并利用染料,进行不同水力负荷下的可视化示踪实验,通过MATLAB处理得到高对比度的流态图像。观察“死区”分布,计算“死区”相对面积用以表征其水力效率。结果表明,湿地装置进水水力负荷较高或较低时,水力效率均较低,且水力负荷较大时更明显;水力分布散度（σ2θ）的大小会对水平潜流人工湿地水力效率造成较大影响;在不同水力负荷下,采用水力学效能（λ）所得到的排序结果相比短路值（s）和有效体积比（e）更能代表实际水平潜流人工湿地的水力效率。     

温度对正渗透工艺性能的影响

正渗透技术是一种以渗透压差为驱动力的新型膜分离工艺。温度是影响正渗透过程的关键因素。为考察温度在工艺运行中的重要作用,研究了温度对正渗透膜特性及工艺性能的影响,探讨通量衰减机制。结果表明,温度影响汲取液动态稀释、浓差极化和膜污染等的效应程度,进而影响正渗透性能。高温能够明显增加水通量和回收率,且汲取液温度影响比原料液显著。因此,合理优化温度条件是降低能耗提高正渗透性能的有效途径。     

水泥窑共处置过程中水泥生料对砷的吸附/冷凝特性

针对水泥生料开展了氮吸附与SEM测试分析,研究了水泥生料的比表面积,孔径结构和微观表面积。同时,利用管式回转炉和控温立式炉联用装置研究了砷元素在水泥生料上的吸附冷凝特性。结果表明,水泥生料的比表面积很小,微观表面结构致密无孔,砷元素主要是冷凝在生料表面上。进入吸附冷凝炉的重金属可以分为3部分,第1部分冷凝在管壁上,占80%左右;第2部分吸附/冷凝在生料上,占10%左右;第3部分随烟气释放到空气中,不到10%。水泥生料对砷的吸附冷凝量随时间的增加而增加,随温度的升高而降低。水泥生料对砷的吸附冷凝特性可用双常数速率方程拟合,拟合效果较好,计算得表观活化能在6~7 kJ/mol之间。此外,砷的初始浓度对水泥生料的吸附冷凝特性影响很小。     

基于主成分和粒子群优化支持向量机的水质评价模型

水质的评价是治理水污染必不可少的工作。为了准确、快速地对水质进行评价,利用主成分分析法从水质监测常见的多个物化指标提取出主成分,然后将主成分作为支持向量分类机的输入,利用历史数据进行水质评价训练并用粒子群算法优化参数,构造出水质评价模型,将从物化指标中得出的主成分代入此模型即可得到水质类别。最后,选取水质监测点实测数据进行试验,结果表明,模型的水质评价结果准确且稳定。     

原铝生产流程温室气体排放主要影响因素的关联度分析

铝是国民经济建设和发展的关键基础材料,然而由其生产过程所产生的大量温室气体排放也逐渐成为政府关注的焦点。本研究计算了我国原铝生产不同年度的生命周期能耗和温室气体排放量,并分析了资源消耗和生产工序能耗等影响因素与温室气体排放的关联性。结果表明,在各年原铝生产的温室气体排放总量中,电力和阳极效应导致的排放所占比重分别为68.5%和7.9%,其他影响因素所占比重均低于6%;与温室气体排放关联度最高的3个影响因素依次是电耗、煤气燃烧和石灰石煅烧,其值分别为0.937、0.899和0.893;在目前铝电耗和阳极效应控制水平提升空间有限的情况下,降低煤气的消耗,提高石灰石的使用效率,是实现原铝生产温室气体减排的有效途径。