Effect of precipitation pH and coexisting magnesium ion on phosphate adsorption onto hydrous zirconium oxide

To understand the effect of precipitation pH and coexisting Mg~(2+) on phosphate adsorption onto zirconium oxide(ZrO_2), ZrO_2 particles precipitated at pH 5.3, 7.1 and 10.5, i.e., ZrO_2(5.3), ZrO_2(7.1)and ZrO_2(10.5), respectively were prepared and characterized, then their adsorption performance and mechanism in the absence and presence of Mg~(2+) were comparatively investigated in this study. The results showed that the Elovich, pseudo-second-order and Langmuir isotherm models correlated with the experimental data well. The adsorption mechanism involved the complexation between phosphate and zirconium. Coexisting Mg~(2+) slightly inhibited the adsorption of phosphate on ZrO_2(5.3), including the adsorption capacity and rate, but coexisting Mg~(2+) greatly increased the adsorption capacity and rate for ZrO_2(7.1)and ZrO_2(10.5). The enhanced adsorption of phosphate on ZrO_2(7.1) and ZrO_2(10.5) in the presence of Mg~(2+) was mainly due to the formation of Mg~(2+)-HPO_4~(2-) ion pair(MgHPO_4~0) in the solution and then the adsorption of MgHPO_4~0 on the adsorbent surface, forming the phosphatebridged ternary complex Zr(OPO_3H)Mg. In the absence of Mg~(2+) , the maximum phosphate adsorption capacity at pH 7 calculated from the Langmuir isotherm model decreased in the order of ZrO 2(7.1)(67.3 mg/g) ZrO_2(5.3)(53.6 mg/g) ≈ ZrO_2(10.5)(53.1 mg/g), but it followed the order of Zr O2(7.1)(97.0 mg/g) ZrO_2(10.5)(79.7 mg/g) ZrO_2(5.3)(51.3 mg/g) in the presence of Mg~(2+) . The results of this work suggest that ZrO_2(7.1) is more suitable for use as an adsorbent for the effective removal of phosphate from municipal wastewater than ZrO_2(5.3) and ZrO_2(10.5),because Mg~(2+) is generally present in this wastewater.     

Nano CuO/g-C3N4 sheets-based ultrafiltration membrane with enhanced interfacial affinity, antifouling and protein separation performances for water treatment application

To improve the interfacial affinity and antifouling properties of polyphenylsulfone(PPSU)membrane, nano CuO/g-C3 N4(g-CN) sheets were synthesized via facile calcination route as one pot synthesis method. The uniformly assembled nanohybrid fillers, CuO on g-CN sheets were confirmed by using XRD, TEM, EDX and FTIR analysis. The non-solvent induced phase inversion technique was used to fabricate the nanohybrid ultrafiltration(UF)membranes by doping different concentration(0.5–1 wt.%) of nano CuO/g-C_3 N_4(g-CN)sheets within the PPSU matrix. The results of contact angle, atomic force microscopy,energy-dispersive X-ray spectroscopy reveal that surface structure and physico-chemical properties of nanohybrid membrane plays lead role in solute interaction and rejection compared to bare membrane, M0. Furthermore, the interfacial affinity of membrane was explored in detail via surface free energy, spreading coefficient, wetting tension and reversible work of adhesion analysis. Nanohybrid UF membrane, with 0.5% of the filler(M1)displayed remarkable permeation flux of 202, 131 L/m2/hr for pure water and protein solution, respectively while maintaining a high protein rejection(96%). Moreover, the exceptional dispersion of the nanosheets in the polymer matrix enhanced FRR(79%) and decreased the overall resistance of M1 compared to the pristine membrane(M0). Overall results suggest that the incorporation of nano sheets is a facile modification technique which improves the comprehensive membrane performance and holds a great potential to be further explored for water treatment.     

Microwave mediated synthesis and characterization of CeO2-GO hybrid composite for removal of chromium ions and its antibacterial efficiency

A facile fabrication and processing of cerium oxide-graphene oxide(CeO_2-GO) hybrid nanocomposites without the use of any surfactant or any organic solvents using chemical method and treatment with microwave irradiation technique are reported. In-situ hexagonal nano cerium oxide particles embedded on the layered surface of GO sheets were investigated for the photodegradation of dyes, removal of chromium Cr(VI) ions and against antibacterial studies. The results imply that hybrid nanocomposites shows enhanced 5-folds of photocatalytic activities in UV(ultraviolet) light irradiation and exhibited rapid efficiency in the elimination of chromium ion better than the pure GO and CeO_2, which are inhibited by competent photosensitive electron inoculation and controlling the electron–hole recombination. The synergetic effect of CeO_2-GO composites played a vital role in showing better results against model bacterium than GO and CeO_2 are due to higher physical interaction endorsed to the stress of membranes acute by piercing edges,large surface area, and higher adsorptive conditions of graphene oxide sheets tailored with ceria particles. The amount of charge transferred at the interface increases with the concentration of O atoms, demonstrating the interaction between CeO_2 and GO is much stronger than CeO_2 and GO are due to the decrease of the average equilibrium distance between the interfaces. The CeO_2-GO interface staggered band alignments existing between the CeO_2 surfaces and GO which shows an excellent synergism. The structure and morphology of composites were tested by X-ray diffraction(XRD), Fourier transform infrared(FTIR), Raman, X-ray photoelectron spectroscopy(XPS), and high-resolution transmission electron microscope(HR-TEM).     

深圳冬季大气气态硝酸和硝酸盐气粒分配特征

利用双通道在线气体和气溶胶分析仪（MARGA）在深圳冬季同时观测了PM_2.5和PM₁₀中水溶性无机离子及气态前体物浓度变化,以探究气态硝酸（HNO₃）和颗粒态硝酸盐（pNO₃^-）的气粒分配特征.结果表明,气态硝酸和颗粒态硝酸盐总和TNO₃（TNO₃=HNO₃+pNO₃^-）中,气态HNO₃、细颗粒NO₃^-和粗颗粒NO₃^-三个部分的占比分别为9.6%、56.8%和33.6%.TNO₃浓度日变化呈现双峰特征,上午峰值来自于细颗粒态NO₃^-增加,由交通早高峰排放NO_x转化生成所致;白天光化学反应使TNO₃的3个部分浓度均增加,TNO₃在下午17：00达到全天峰值.相关分析表明,低温有利于NO₃^-以NH₄NO₃存在于细颗粒态;TNO₃浓度较高时,细颗粒态NO₃^-占比亦升高.     

活性污泥中一氧化氮还原酶的提取和测定优化

通过正交实验,研究了超声破碎法和低温高压破碎法提取一氧化氮还原酶（nitric oxide reductase,nor）的活性,分析了超声强度和次数,破碎压力和次数,裂解液的添加量等因素对于胞内可溶性蛋白和核酸（DNA）的释放与提取nor活性的影响.根据活性污泥中酶的催化特性以及其他实验条件,完善了nor催化活性的测定方法.结果表明超声法提取nor的参数应设定为,超声次数为100次,超声强度为500W,裂解液的添加量为0.1mL.低温高压破碎法提取nor的参数应设定为破碎次数为4次,破碎压力为50MPa,裂解液的添加量为0.1mL.低温高压破碎法下的胞内可溶性蛋白和DNA的释放量与nor的最大催化活性要高于超声破碎法.此外,在nor催化活性的测定方法中,nor活性测定终点时间应为15min.     

Effects of phosphate on the transport of graphene oxide nanoparticles in saturated clean and iron oxide-coated sand columns

In this study, transport behaviors of graphene oxide (GO) in saturated uncoated (i.e., clean sand) and goethite-coated sand porous media were examined as a function of the phosphate. We found that phosphate enhanced the transport of GO over a wide range of solution chemistry (i.e., pH 5.0–9.0 and the presence of 10 mmol/L Na⁺ or 0.5 mmol/L Ca²⁺). The results were mainly ascribed to the increase of electrostatic repulsion between nanoparticles and porous media. Meanwhile, deposition site competition induced by the retained phosphate was another important mechanism leading to promote GO transport. Interestingly, when the phosphate concentration increased from 0.1 to 1.0 mmol/L, the transport-enhancement effect of phosphate in goethite-coated sand was to a much larger extent than that in clean sand. The observations were primarily related to the difference in the total mass of retained phosphate between the iron oxide-coated sand and clean sand columns, which resulted in different degrees of the electrostatic repulsion and competitive effect of phosphate. When the background solution contained 0.5 mmol/L Ca²⁺, phosphate could be bind to sand/ goethite-coated sand surface by cation bridging; and consequently, promoted competition between phosphate and nanoparticles for deposition sites, which was an important mechanism for the enhanced effect of phosphate. Moreover, the DLVO theory was applicable to describe GO transport behaviors in porous media in the absence or presence of phosphate. Taken together, these findings highlight the important status and role of phosphate on the transport and fate of colloidal graphene oxide in the subsurface environment.     

GO-TiO2改性PVDF复合膜去除微污染水体中氨氮

以氧化石墨烯（GO）、二氧化钛（TiO₂）和氧化石墨烯-二氧化钛（GO-TiO₂）为改性物质,借助真空过滤法对聚偏氟乙烯（PVDF）微滤膜进行改性制备复合膜.利用接触角测量仪、扫描电子显微镜、傅里叶红外变换光谱、X射线粉末衍射仪等手段探究了复合膜的结构和亲水性.同时选用腐殖酸（HA）作为水中微污染物的代表考察了复合膜的抗污染性能.选择常州滆湖支浜水样作为原水,研究了复合膜在黑暗及紫外光条件下对氨氮的去除效果.结果表明,GO、TiO₂和GO-TiO₂（GT）复合膜均具有优于PVDF膜的亲水性和抗污染性能,黑暗条件下,GO浓度为1mg/mL的GO复合膜氨氮去除率最高,达到26.4%;紫外光条件下,GO和TiO₂间存在协同作用,GO-TiO₂浓度为1mg/mL、GO/TiO₂=3：1的GT复合膜氨氮去除效率达到最佳（58.2%）.     

Fe3O4/GO对水溶液中Cd(II)去除的影响因素

为探索高效且快速去除水溶液中Cd （Ⅱ）污染方法,采用自制磁性四氧化三铁负载氧化石墨烯（Fe₃O₄/GO）纳米复合材料对水溶液中Cd （Ⅱ）进行去除,利用单因素实验确定影响因素水平范围（初始Cd （Ⅱ）浓度、温度、反应时间、初始pH值）,并采用响应面法（RSM）及人工神经网络-遗传算法（ANN-GA）对去除水溶液中Cd （Ⅱ）的影响因素（4因素3水平）进行优化,利用等温吸附、动力学及热力学参数研究吸附剂性能.通过扫描电子显微镜（SEM）、X射线衍射仪及超导量子干涉器件（SQUID）对复合材料表征.结果表明,平均粒径为30.9nm的磁性Fe₃O₄/GO纳米复合材料被成功制备.RSM用于磁性Fe₃O₄/GO纳米复合材料对水溶液中Cd （Ⅱ）去除条件优化,预测去除率达到86.451%,验证试验为82.220%,对应条件：温度为20.14℃,反应时间为57.78min,初始pH值为6.41和初始Cd （Ⅱ）浓度为11.18mg/L; ANN-GA优化条件后的预测去除率为89.722%,验证试验为87.723%,相应条件：温度为29.96℃,pH值为5.49,初始Cd （Ⅱ）浓度为28.36mg/L,反应时间为65.78min.根据模型R²值,预测的最大去除率及验证试验,ANN-GA模型性能及预测能力均高于RSM.RSM方差分析表明4个因素对磁性Fe₃O₄/GO纳米复合材料去除水溶液中Cd （Ⅱ）的影响大小为：初始Cd （Ⅱ）浓度>温度>反应时间>pH值.吸附机理分析结果显示,Fe₃O₄/GO纳米复合材料对Cd （Ⅱ）吸附过程同时存在着物理吸附和化学吸附.结合ANN-GA优化,利用磁铁实现且快速分离,磁性Fe₃O₄/GO纳米复合材料用于去除Cd （Ⅱ）是可行的.关键字：Cd （Ⅱ）;四氧化三铁负载氧化石墨烯;单因素实验;响应面法;人工神经网络-遗传算法中图分类号：X53     

锰铝双氧化物改性生物炭减缓土壤重金属对黑麦草的毒性作用

电子垃圾拆解过程中引起的土壤重金属铜(Cu)和镉(Cd)复合污染现象成为一个严峻的问题,为了解决这一问题,利用废弃的螃蟹壳生物质与锰铝盐进行共沉淀后共热解制备了螃蟹壳生物炭(BC)和片状锰铝双氧化物改性的螃蟹壳生物炭(LDO/BC)材料.污染土壤经过BC和LDO/BC修复后,土壤pH、有效磷、速效钾和酶活性得到了提升,土壤中的DTPA-Cu和DTPA-Cd含量显著降低.微生物群落分析表明BC-1%能促进Gemmatimonadota(芽单胞菌)和Acidobacteriota(酸杆菌)相对丰度的上升,而LDO/BC-1%能促进Proteobacteria(变形菌)相对丰度的上升,且变形菌有利于减少Cd在植物中的积累作用.在修复后的土壤中种植黑麦草培养28 d,结果表明,经过投加量为5%BC和1%LDO/BC分别修复后土壤种植的黑麦草发芽率分别提高29%和60%,生长状况更佳,并且黑麦草植株内Cu和Cd的含量相对于未经生物炭材料处理的空白组显著降低.LDO/BC-1%处理组相对于其他处理组表现出更优异的修复效果,且负载在LDO/BC上的Mn可以有效地降低黑麦草吸收土壤中的重金属Cd.     

椰纤维生物炭及其硝酸改性对稻田土壤中Pb钝化的影响

通过土壤培养实验,并结合扫描电镜(SEM)、 X射线光电子能谱(XPS)、同步辐射X射线荧光(μ-XRF)和傅立叶变换红外吸收光谱(FTIR)等光谱学技术,探明椰纤维生物炭(CFB)和硝酸改性椰纤维生物炭(NCFB)对稻田土壤钝化外源铅(Pb)的效果及其内在机制.与CFB相比,NCFB蜂窝状孔内壁更粗糙,且硝酸改性后CFB表面含C—O结构的醇酚醚类官能团量明显降低,含■结构的羧基类的官能团量明显增加.相较于培养150 d后的对照(不添加生物炭)稻田土壤,添加CFB和NCFB的稻田土壤中EDTA提取态Pb含量分别降低了39.7%和105.4%.添加NCFB的土壤中碳酸盐结合态和铁锰氧化物结合态Pb含量显著降低且有机结合态和残渣态Pb含量则显著升高,SRXRF扫描结果可知外源Pb在富含Ca和Cu元素的CFB颗粒微区大量富集,在富含Fe、 Mn和Ti元素的土壤团聚体微区富集相对较少.另外,培养实验中,相较于无外源Pb时A-CFB和A-NCFB,有外源Pb时A-CFB_Pb和A-NCFB_Pb中的羧酸盐特征峰(1 384 cm^-1)...