柱撑蒙脱石吸附与催化降解黄药的特性研究

以黄药水溶液为模拟对象,分别考察了粘土用量、吸附时间以及黄药初始浓度等参数对柱撑蒙脱石吸附黄药的影响,结果表明,改性后蒙脱石的结构变化对改善其吸附能力起到了关键作用,有机柱撑剂不仅改变了复合柱撑粘土中蒙脱石原有的亲水特性,合柱撑蒙脱石具有吸附速度快和吸附容量大的特点,同时改善了层间距中无机柱撑剂的物化特性,使得复并且提高了其催化性能。     

有机-无机复合改性蒙脱石同时吸附水中苯酚和铬(Ⅵ)

以钠基蒙脱石(Na-MMT)为原料,采用十六烷基三甲基溴化铵(CTMAB)预先改性,然后进行羟基铝柱撑改性,以制备不同CTMAB含量的有机-无机复合蒙脱石(CTMAB-Al-MMT),用于同时对水中苯酚和铬(Ⅵ)的吸附.采用XRD、FTIR表征复合改性蒙脱石.研究结果表明,CTMAB和羟基铝阳离子有效进入蒙脱石层间,且层间距随CTMAB加载量增大而增加.吸附时间、溶液pH和投剂量等因素对吸附率的影响显著,在混合溶液的苯酚、铬(Ⅵ)初始浓度均为30 mg·L-1,投剂量0.6 g/50 mL,pH=6,以及吸附时间2 h时,苯酚和铬(Ⅵ)吸附去除率分别达85.0%和94.7%,表明制备的复合改性蒙脱石具有能有效同时吸附水中苯酚和铬(Ⅵ)的良好性能.复合改性蒙脱石对苯酚、铬(Ⅵ)的等温吸附可用Langmuir方程和Freundlich方程来拟合,对苯酚的吸附符合Freundlich方程,相关系数为0.9946,对铬(Ⅵ)的吸附符合Langmuir方程,相关系数为0.9989.     

蒙脱石吸附Cr3+、Cd2+、Cu2+、Pb2+、Zn2+的研究:pH值和有机酸的影响

粘土具有良好的离子交换和吸附特性，常被用作垃圾填埋场的衬层，吸附垃圾渗滤液中的氨氮及重金属离子，防止污染土壤和地下水。研究了pH值对蒙脱石吸附Cr^3 、Cd^2 、Cu^2 、Pb^2 和Zn^2 等五种重金属离子的影响，以及有化学络合剂EDTA和几种有机酸存在条件下，蒙脱石吸附Cr^3 、Cd^2 、Cu^2 、Pb^2 和Zn^2 五种重金属离子的效果。为了接近自然吸附状态，实验采用了离子交换柱进行连续吸附。结果表明，pH值对Cu^2 、Pb^2 和Cu^2 的吸附率影响极大；化学络合剂以及有机酸的存在降低了各重金属离子的吸附率，影响的强弱(设其符号为y)顺序为Y(Pb^2 )≤y(Cd^2 )≤y(Zn^2 )≤y(Cu^2 )≤y(Cr^3 )。     

不同改良剂对铜矿尾矿砂的改良效果研究

研究了用蒙脱石、稻草和鸡粪作为改良剂对铜矿尾矿砂有效养分、有效态重金属含量、pH值以及对尾矿砂上黑麦草生长的影响。结果表明：（1）蒙脱石可显著提高尾矿砂对铵态氮的保留能力；（2）施肥可降低尾矿砂的pH值，施用鸡粪可使尾矿砂pH值下降约1个单位，而添加蒙脱石和稻草对尾矿砂pH值未产生明显影响；（3）添加蒙脱石可使尾矿砂中铜、锌的有效态含量降低，而添加稻草和鸡粪则使其有效态重金属含量增高;(4）随改良剂添加量的增加，蒙脱石和鸡粪处理组黑麦草吸收铜、锌的量减少而稻草处理组则增加；（5）3种改良剂可明显影响尾矿砂上黑麦草的生长状况。     

菲高效降解菌的降解特性及其受蒙脱石的影响研究

通过选择性富集培养与纯化,从广州油制气厂附近的污染土壤中分离获得一株能以菲为唯一碳源和能源,快速生长的优势菌株（编号为YZ-1）。16S rDNA序列分析结果表明,YZ-1菌株为琼氏不动杆菌（Acinetobacter junii）。当无机盐培养液中菲初始质量浓度为100mg·L-1时,45h内该菌株对菲的降解率可达到99.5%。YZ-1菌株的最佳生长条件为pH7.4,温度30℃,摇床转速160r·min-1。加入蒙脱石矿物之后,在降解的初期（前16h）表现为促进菲的生物降解作用,但随着时间的延长,菲的降解速率逐渐低于不加蒙脱石体系,并随蒙脱石含量或菲质量浓度的增加,此抑制延缓现象愈加明显。矿物对高浓度的菲具有吸附分散作用,而对低浓度的菲具有吸附保护作用。     

细滤膜处理高浓废工业废液浓差极化与膜污染

当利用纳滤膜处理高浓度工业废液时，实验研究表明随着浓缩时间的延长，渗透液通量衰减系数和膜污染阻力提高很快；浓缩时间较短时，纳滤膜的分离过程由浓差极化控制；浓缩时间较长时，纳滤膜分离过程由浓差极化和膜污染共同控制；提高卷式纳滤膜浓缩液流量会增加纳滤膜浓差极化与膜污染的影响，板式纳滤膜恰与此相反；原浓度高的母液，其渗透液通量衰减系数和膜污染阻力随浓缩时间的延长其提高速率相对也高。     

不同改良剂对铜矿尾矿砂的改良效果研究

研究了用蒙脱石、稻草和鸡粪作为改良剂对铜矿尾矿砂有效养分、有效态重金属含量、pH值以及对尾矿砂上黑麦草生长的影响。结果表明 :(1 )蒙脱石可显著提高尾矿砂对铵态氮的保留能力 ;(2 )施肥可降低尾矿砂的pH值 ,施用鸡粪可使尾矿砂pH值下降约 1个单位 ,而添加蒙脱石和稻草对尾矿砂pH值未产生明显影响 ;(3 )添加蒙脱石可使尾矿砂中铜、锌的有效态含量降低 ,而添加稻草和鸡粪则使其有效态重金属含量增高 ;(4 )随改良剂添加量的增加 ,蒙脱石和鸡粪处理组黑麦草吸收铜、锌的量减少而稻草处理组则增加 ;(5 ) 3种改良剂可明显影响尾矿砂上黑麦草的生长状况     

乳状液膜法迁移及分离铬(Ⅵ)的研究

本文采用以叔胺N7301为流动载体、兰113A为表面活性剂、煤油为膜溶剂、NaOH作内相试剂的乳状液膜体系迁移分离铬(Ⅵ).研究了其迁移机理,确定了适宜制乳、迁移分离及破乳等有关条件,实验表明,不同浓度的含铬(Ⅵ)水样经液膜处理后,其含铬(Ⅵ)量均降至0.5μg·ml~(-1)以下,低于国家排放标准.     

改良剂对铜矿尾矿砂与菜园土混合土壤性质及黑麦草生长的影响

用蒙脱石、稻草、鸡粪作为改良剂，研究不同改良剂对铜矿尾矿砂与菜园土混合土壤PH、有效态重金属含量、脲酶和磷酸酶活性以及混合土壤上种植的黑麦草生长的影响。结果表明：添加蒙脱石对不同生长期黑麦草的生长量没有显著影响；使用稻草和鸡粪处理尽管在开始阶段不利于黑麦草(第1茬和第2茬)的生长，但随时间延长，黑麦草的生物量(第3茬和第4茬)明显增加，表现出很好的后效。黑麦草的根重与鸡粪的添加量关系显著，施用稻草的纯尾矿砂处理组(处理22)根重最大，而且蚯蚓只能在使用适量稻草的处理条件下才能在混合土壤中生长。土壤酶的分析发现，磷酸酶的活性除了在蚯蚓能够生长的处理组表现出较高外，其它处理之间无明显差异，但脲酶的活性则随着稻草和鸡粪施用量的增加而显著提高。各处理之间土壤的PH值变化不大。添加稻草减少了土壤中有效态重金属的含量，而使用鸡粪处理明显增加了土壤中包括铜、铅和锌等有效态重金属的含量，说明在施用含有重金属的畜禽粪便时务必小心谨慎，以防二次污染。     

三氯乙烯在模型吸附剂上的吸附特性

为了分别揭示矿物质、有机质在疏水性有机物吸附中的作用,文章研究了蒙脱石、高岭土、硅胶以及用腐殖酸修饰后的这3种模型吸附剂对三氯乙烯的吸附行为。采用批量吸附实验方法分别研究了三氯乙烯在不同吸附剂上的吸附。结果表明,硅胶、高岭土、蒙脱石对三氯乙烯均具有一定的吸附能力,吸附系数Kd值分别为10.3、3.13、1.15L·kg-1,硅胶的吸附能力明显高于高岭土和蒙脱石。3种无机模型吸附剂对腐殖酸表现出不同的吸附能力,蒙脱石最强,高岭土次之,硅胶最差,与对三氯乙烯的吸附能力正好相反。被腐殖酸修饰后3种模型吸附剂对三氯乙烯的吸附都明显增强,但增强程度不一样,当用8%腐殖酸(腐殖酸与模型吸附剂的质量比)修饰后,3种吸附剂对三氯乙烯的吸附Kd值均在23L·kg-1左右。虽然Kd随有机质的质量分数增高而上升,但是Kd值与有机质的质量分数不存在线性相关关系,特别是对于具有较高吸附能力的无机吸附剂,说明无机矿物本身结构对于吸附起到同等重要的作用。     

Improvement of detection method of and in reclaimed water

Cryptosporidium and Giardia are two typical species of pathogenic protozoans that seriously endanger water quality. Previous works indicated that detection of Cryptosporidium and Giardia with modified United States Environmental Protection Agency (USEPA) method-1623 using a membrane filtration-elution for sample concentration attained better recovery and lower cost compared to the USEPA method-1623. Several improvements of membrane filtration-elution step as well as immunomagnetic separation (IMS) steps were investigated and an optimized method for detection of Cryptosporidium and Giardia in wastewater reclamation system was recommended in this paper. The experimental results show that an overnight soak of the membrane after scraping and vortex agitation before elution could enhance and stabilize the recovery. Increasing turbidity to 4 NTU by adding kaolin clay before filtration could effectively improve the recovery of low-turbidity water. Washing the concentrate after centrifugation and twice acid dissociation both reduced the impact of water quality to protozoan recovery. Protozoans in different water samples were determined by this optimized method, and the recovery of Cryptosporidium and Giardia were above 70% and 80% respectively, much higher than the acceptance of method-1623.     

Improvement of detection method of Cryptosporidium and Giardia in reclaimed water

Cryptosporidium and Giardia are two typical species of pathogenic protozoans that seriously endanger water quality. Previous works indicated that detection of Cryptosporidium and Giardia with modified United States Environmental Protection Agency (USEPA) method-1623 using a membrane filtration-elution for sample concentration attained better recovery and lower cost compared to the USEPA method-1623. Several improvements of membrane filtration-elution step as well as immunomagnetic separation (IMS) steps were investigated and an optimized method for detection of Cryptosporidium and Giardia in wastewater reclamation system was recommended in this paper. The experimental results show that an overnight soak of the membrane after scraping and vortex agitation before elution could enhance and stabilize the recovery. Increasing turbidity to 4 NTU by adding kaolin clay before filtration could effectively improve the recovery of low-turbidity water. Washing the concentrate after centrifugation and twice acid dissociation both reduced the impact of water quality to protozoan recovery. Protozoans in different water samples were determined by this optimized method, and the recovery of Cryptosporidium and Giardia were above 70% and 80% respectively, much higher than the acceptance of method-1623.     

水中痕量亚当氏剂和二苯胺的固相微萃取方法研究

研究了固相微萃取(SPME)-高效液相色谱(HPLC)测定水样中痕量亚当氏剂和二苯胺的分析方法.对SPME的条件如萃取纤维、萃取时间、萃取温度、离子强度、解吸方式、解吸溶剂、解吸时间进行了优化,并用于地下水等实际水样的分析.SPME优化的条件为:选用60μmPDMS/DVB萃取纤维在室温25℃下直接萃取60min,磁力搅拌速度为1100r.min-1,然后萃取纤维在解吸室内静态解吸9min后进行HPLC分析.液相色谱分离条件为ZORBAXSBC18柱(4.6mmi.d.×250mm,5.0μm),流动相为甲醇-水(70:30,V/V),流速为1.0ml.min-1,二极管阵列检测器波长为280nm.方法线性范围为0.005mg.l-1—0.5mg.l-1(R>0.99),两种物质的检出限(S/N=3)分别为0.003mg.l-1和0.002mg.l-1.加标回收率分别在89.6%—100.4%和97.5%—100.1%(n=5)之间,相对平均标准偏差(RSD)分别在4.5%—6.2%和3.8%—6.7%之间.该方法快速、简便,无需使用有机溶剂,适于水样中痕量物质的分析.     

An antifouling catechol/chitosan-modified polyvinylidene fluoride membrane for sustainable oil-in-water emulsions separation

• Underwater superoleophobic membrane was fabricated by deposition of catechol/chitosan. • The membrane had ultrahigh pure water flux and was stable under harsh pH conditions. • The membrane exhibited remarkable antifouling property in O/W emulsion separation. • The hydration layer on the membrane surface prevented oil droplets adhesion. Low-pressure membrane filtrations are considered as effective technologies for sustainable oil/water separation. However, conventional membranes usually suffer from severe pore clogging and surface fouling, and thus, novel membranes with superior wettability and antifouling features are urgently required. Herein, we report a facile green approach for the development of an underwater superoleophobic microfiltration membrane via one-step oxidant-induced ultrafast co-deposition of naturally available catechol/chitosan on a porous polyvinylidene fluoride (PVDF) substrate. Membrane morphology and surface chemistry were studied using a series of characterization techniques. The as-prepared membrane retained the original pore structure due to the ultrathin and uniform catechol/chitosan coating. It exhibited ultrahigh pure water permeability and robust chemical stability under harsh pH conditions. Moreover, the catechol/chitosan hydrophilic coating on the membrane surface acting as an energetic barrier for oil droplets could minimize oil adhesion on the surface, which endowed the membrane with remarkable antifouling property and reusability in a cyclic oil-in-water (O/W) emulsion separation. The modified membrane exhibited a competitive flux of ~428 L/(m²·h·bar) after three filtration cycles, which was 70% higher than that of the pristine PVDF membrane. These results suggest that the novel underwater superoleophobic membrane can potentially be used for sustainable O/W emulsions separation, and the proposed green facile modification approach can also be applied to other water-remediation materials considering its low cost and simplicity.     

Comparison of CNT-PVA membrane and commercial polymeric membranes in treatment of emulsified oily wastewater

CNT-PVA membrane was fabricated and compared with polymeric membranes. The separation performance was evaluated by homemade and cutting fluid emulsions. The three membranes show similar oil retention rates. CNT-PVA membranes have higher permeation fluxes compared with polymeric membranes. CNT-PVA membrane shows higher fouling resistance. Membrane separation is an attractive technique for removal of emulsified oily wastewater. However, polymeric membranes which dominate the current market usually suffer from severe membrane fouling. Therefore, membranes with high fouling resistance are imperative to treat emulsified oily wastewater. In this study, carbon nanotube-polyvinyl alcohol (CNT-PVA) membrane was fabricated. And its separation performance for emulsified oily wastewater was compared with two commercial polymeric membranes (PVDF membrane and PES membrane) by filtration of two homemade emulsions and one cutting fluid emulsion. The results show that these membranes have similar oil retention efficiencies for the three emulsions. Whereas, the permeation flux of CNT-PVA membrane is 1.60 to 3.09 times of PVDF membrane and 1.41 to 11.4 times of PES membrane, respectively. Moreover, after five consecutive operation circles of filtration process and back flush, CNT-PVA membrane can recover 62.3% to 72.9% of its initial pure water flux. However, the pure water flux recovery rates are only 24.1% to 35.3% for PVDF membrane and 6.0% to 26.3% for PES membrane, respectively. Therefore, CNT-PVA membrane are more resistant to oil fouling compared with the two polymeric membranes, showing superior potential in treatment of emulsified oily wastewater.     

Hydrophilic/underwater superoleophobic graphene oxide membrane intercalated by TiO2 nanotubes for oil/water separation

GO/TiO₂ membrane was prepared by assembling GO nanosheets and TiO₂ nanotubes. The intercalation of TiO₂ nanotubes enlarged the space of GO interlayers and modified the surface morphology. Hydrophilic/underwater superoleophobic property of GO/TiO₂ membrane was obtained. Water permeability, hydrophilicity, oleophobicity and antifouling ability of GO-based membrane were all enhanced by intercalating TiO₂ nontubes. Membrane technology for oil/water separation has received increasing attention in recent years. In this study, the hydrophilic/underwater superoleophobic membrane with enhanced water permeability and antifouling ability were fabricated by synergistically assembling graphene oxide(GO) nanosheets and titanium dioxide (TiO₂) nanotubes for oil/water separation. GO/TiO₂ membrane exhibits hydrophilic and underwater superoleophobic properties with water contact angle of 62° and under water oil contact angle of 162.8°. GO/TiO₂ membrane shows greater water permeability with the water flux up to 531 L/(m²·h·bar), which was more than 5 times that of the pristine GO membrane. Moreover, GO/TiO₂membrane had excellent oil/water separation efficiency and anti-oil-fouling capability, as oil residual in filtrate after separation was below 5 mg/L and flux recovery ratios were over 80%.The results indicate that the intercalation of TiO₂ nanotubes into adjacent GO nanosheets enlarged the channel structure and modified surface topography of the obtained GO/TiO₂ membranes, which improved the hydrophilicity, permeability and anti-oil-fouling ability of the membranes, enlightening the great prospects of GO/TiO₂ membrane in oil-water treatment.     

乙酸对硅酸聚合胶凝及形态分布的影响

要研究了硅酸在不同pH条件下,乙酸存在时的形态分布及转化特征．结果表明：当硅酸溶液中有乙酸存在时,硅酸的聚合胶凝时间将延长．从而证实了乙酸的存在,能有效地减缓硅酸溶液中聚硅酸的生长速度．     

聚乙烯醇精馏残渣组分分析及其环境风险评价

为评估聚乙烯醇生产中精馏残渣组分及其环境污染风险,为此类危险废物的环境管理提供技术支持,采集华东某聚乙烯醇生产企业的精馏残渣,分析其重金属以及有机污染物含量,并评估其环境风险。研究结果表明聚乙烯醇精馏残渣主要来自生产环节中的醋酸乙烯精制工段,残渣中的有机物组分主要为醋酸及其他有机酸类,其中醋酸的相对含量达到63.47%;残渣中的重金属主要包括Zn、Ni和Cr,其含量分别为404 537 mg·kg-1,8 654 mg·kg-1和5 084 mg·kg-1。环境风险评价的结果表明残渣中有机物污染物引起的环境风险在可接受范围内,而重金属污染严重,同时有很高潜在生态风险。精馏残渣中的主要环境污染风险因子为醋酸、Zn和Ni。     

Release of sex pheromone and its precursors in the pine sawfly Diprion pini (Hym., Diprionidae)

Summary. The first identification of a sex pheromone of a pine sawfly (Hymenoptera, Diprionidae) dates back almost thirty years. Since then, female-produced pheromones of over twenty diprionid species have been investigated by solvent extraction followed by separation and identification. However, no study has shown what the females actually release. Collection of airborne compounds using absorbtion on charcoal filter as well as solid phase microextraction (SPME) followed by analysis employing gas chromatography combined with mass spectrometry (GC-MS), revealed an unusual system in Diprion pini, in which the pheromone precursor alcohol, 3,7-dimethyl-2-tridecanol, is released together with acetic, propionic, butyric and isobutyric acids. The corresponding acetate, propionate and butyrate esters of 3,7-dimethyl-2-tridecanol were also found in the samples. All esters were electrophysiologically active, and the propionate and isobutyrate were attractive in trapping experiments. Based on these and earlier reported results, it seems that at least in part of its range, the pheromone response of D. pini is not very specific with regard to the functional group, as long as this is an ester.     

乳状液膜法分离提取醋酸的模拟试验

研究了LMS－2－煤油－NaOH液膜体系处理醛酸水溶液的最佳操作条件，讨论了表面活性剂浓度、搅拌速度、试剂比、油内比及乳水比对提取率的影响，得出了制乳的最佳稳定条件，提取率可达96％以上。