Polymer hydrogels with enhanced stability and heterogeneous Fenton activity in organic pollutant removal

Polymer hydrogel-based materials have been shown to act as novel Fenton catalysts for water treatment, but the rational design of hydrogel-based catalysts with good stability has been a great challenge. To increase the stability and activity of polymer-based Fenton catalysts, uniform urchin-like α-Fe_2O_3 was grown in situ in a PVA carrier matrix here. PVA molecules promoted the growth of urchin-like α-Fe_2O_3, and then the PVA hydrogel acted as a barrier and carrier to reduce agglomeration. Through coordination by hydroxyl groups,PVA had good combination with Fe ions and α-Fe_2O_3. The formation of Fe–O–C bonds between iron oxides and polymers was reported for the first time, enhancing the material stability during catalysis. Under higher PVA concentrations, the resulting composite hydrogel could generate more ˙OH due to the increase in the number of active sites because of the hairy urchin-like structure. In tetracycline degradation through a heterogeneous Fenton reaction, the resulting material had good catalytic activity from pH 2 to pH 10 with low iron leaching, good reusability and remained at a level of nearly 90%after five consecutive cycles. Density functional theory calculations were used to further prove the mechanism of structural change of the iron oxides. The HOMO and LUMO energies of the iron oxides changed from 5.428 and 4.899 eV to 5.926 and 5.310 eV,indicating that the presence of PVA could influence the charge of the iron atom. The results provide new insights into the preparation of polymer hydrogel-based heterogeneous Fenton catalysts with enhanced stability for water treatment.     

舟山近岸海域沉积物中重金属的生物有效性研究

对舟山附近海域沉积物中的酸可挥发性硫化物（AVS）、同步提取重金属（SEM）和5种重金属的分布进行了调查,并用（SEM-AVS）差值法对上述重金属的生物有效性进行了研究。结果表明,该海域表层沉积物中AVS和SEM含量均较低,AVS含量范围为0.005~4.21 μmol/g,平均含量为0.546 μmol/g,SEM含量范围为0.3356~1.614 μmol/g,平均含量为0.7998 μmol/g;表层沉积物中Cu、Pb、Zn、Cr和Cd的平均含量分别为24.65×10-6、27.21×10-6、114.5×10-6、58.26×10-6和0.142×10-6。（SEM-AVS）差值法的结果表明除5个站位外,其余站位沉积物中重金属对生物可能具有中等毒性。     

一种通用的海洋环境监测系统设计方法

提出一种通用的海洋环境监测系统设计方法,将海洋环境监测系统分为采集层、数据层以及应用层三个层次,并分别描述了三层中采用的关键技术,采集程序结合配置工具可以灵活地实现多源异构数据的获取,数据库可以无更改地满足新的存储需求,基于功能模块库实现应用客户端的快速生成。该方法已应用在基于国际海洋标准IEEE P2402的监测系统开发中,通过不同的监测系统开发案例,展示了该方法的可行性及有效性。     

One-step synthesis of Cu(II) metal–organic gel as recyclable material for rapid, efficient and size selective cationic dyes adsorption

Efficient removal of non-biodegradable and hazardous dyes from wastewater remains a hot research topic. Herein, a rationally designed a Cu(Ⅱ)-based metal–organic gel(Cu-MOG) with a nanoporous 3 D network structure prepared via a simple one-step mixing method was successfully employed for the removal of cationic dyes. The Cu-MOG exhibited high efficiency, with an adsorption capacity of up to 650.32 mg/g, and rapid adsorption efficiency, with the ability to adsorb 80% of Neutral Red within 1 min. The high adsorption efficiency was attributed to its large specific surface area, which enabled it to massively bind cationic dyes through electrostatic interaction, and a nanoporous structure that promoted intra-pore diffusion. Remarkably, the Cu-MOG displayed size-selective adsorption, based on adsorption studies concerning dyes of different sizes as calculated by density functional theory. Additionally, the adsorption performance of the Cu-MOG still maintained removal efficiency of 100% after three regeneration cycles. These results suggested that the Cu-MOG could be expected to be a promising and competitive candidate to conveniently process wastewater.     

Highly catalytic activity of Mn/SBA-15 catalysts for toluene combustion improved by adjusting the morphology of supports

Rod-like, hexagonal and fiber-like SBA-15 mesoporous silicas were synthesized to support MnO_x for toluene oxidation. This study showed that the morphology of the supports greatly influenced the catalytic activity in toluene oxidation. MnO_x supported on rod-like SBA-15(R-SBA-15) displayed the best catalytic activity and the conversion at 230°C reached more than 90%, which was higher than the other two catalysts. MnO_x species consisted of coexisting MnO_2 and Mn_2O_3 on the three kinds of SBA-15 samples. Large amounts of Mn_2O_3 species were formed on the surface and high oxygen mobility was obtained on MnO_x supported on R-SBA-15, according to the H_2 temperature programmed reduction(H_2-TPR)and X-ray photoelectron spectroscopy(XPS) results. The Mn/R-SBA-15 catalyst with greater amounts of Mn_2O_3 species possessed a large amount of surface lattice oxygen, which accelerated the catalytic reaction rate. Therefore, the surface lattice oxygen and high oxygen mobility were critical factors on the catalytic activity of the Mn/R-SBA-15 catalyst.     

Ag/P-g-C3N4复合材料可见光催化降解双酚AF的机理研究

利用简单的热聚合及原位沉淀法制备了一系列不同质量比(1%～10%)的Ag/P-g-C_3N_4复合材料,采用XRD、SEM、TEM、UV-Vis DRS、FTIR、BET和XPS等表征手段对复合材料的形貌结构、光学特性和化学组成进行了表征.利用合成材料光催化降解双酚AF(BPAF),研究了溶液初始pH、溶解性有机质(DOM)对BPAF降解的影响,并对光催化降解机理进行了探讨.结果表明,在pH=7时,5%Ag/P-g-C_3N_4表现出最强的光催化性能,其在90 min内对BPAF的降解率达到100%.DOM在低浓度(0.5 mg·L~(-1))时促进了BPAF的光降解,而在高浓度时(2～10 mg·L~(-1))抑制了BPAF的光降解.活性基团捕获实验结果表明,在Ag/P-g-C_3N_4降解BPAF过程中,h~+和·OH起主要的作用,直接参与了BPAF的降解.相对于P-g-C_3N_4,Ag/P-g-C_3N_4光催化性能的增强主要是因为Ag的负载促进了e~-和h~+的分离,同时Ag单质的SPR效应提高了复合材料对可见光的吸收率,延长了光生载流子的寿命.     

中国水土资源本底匹配状况研究

论文以中国水资源二级区为基本单元,利用单位面积水资源量法和基尼系数法,以二级区水资源总量和潜在可开垦耕地面积为数据基础,评价中国水土资源本底匹配状况,为中国水土资源优化配置提供科学依据。首先根据适宜农作物耕种的高程、坡度和土壤类型条件,得到中国潜在可开垦耕地分布;然后,计算单位潜在可开垦耕地面积水资源量,评价中国水土资源本底匹配分布状况;最后,绘制水土资源洛伦兹曲线,计算基尼系数,对中国水土资源本底匹配总体状况进行评价。研究结果表明： 1）中国北部区域潜在可开垦耕地较多,西南部和南部沿海区域分布较少,未来具有较大耕地开发潜力的区域主要分布在北方; 2）中国本底水资源和潜在可开垦耕地资源空间分布存在严重错位; 3）较之已有研究成果中依据水资源量和耕地面积计算的基尼系数0.566,论文以本底水资源和潜在耕地为基础数据计算的基尼系数0.712要大很多,表征中国本底水土资源不匹配程度要严重得多,中国80%的水资源服务不到23%的潜在可开垦耕地。     

基于CSGD的排放清单处理工具研究

CSGD（crowd sourcing geographic data,众源地理数据）是通过互联网向大众或相关机构提供的一种开放地理空间数据,具有易获取、时效性好、准确性高等特点,在排放清单时空分配方面具有应用潜力.然而,现有排放清单处理工具不支持CSGD数据直接输入且难以满足排放清单空间分配和空气质量模式所需清单格式,因此,亟待开发一套可以拓展该类数据在排放清单领域应用的工具.以CSGD中的POI（城市设施兴趣点）数据为主要研究对象,基于QGIS平台、C++语言及Python语言,开发了在Windows系统下的ISAT（inventory spatial allocate tool,排放清单空间分配工具）工具及在Windows或Linux系统下的ISAT.M工具.结果表明:ISAT工具以POI数据为基础制作出的空间分配结果与排放源排放强度的空间分布特征的一致性较好;ISAT.M工具输出的inline清单可以作为CMAQ空气质量模式及其DDM敏感性分析模块的输入文件并开展模拟,通过与SMOKE模型的关闭源法模拟结果对比发现,二者在数据及空间分布上呈较好的一致性.研究显示,CSGD数据应用于排放清单空间分配可较好地反映排放源空间分布特征,同时由于此类数据存在信息冗杂、近郊区数据缺失等问题,在应用过程中应注意数据清洗及数据种类的选取工作.      

两种生物炭的制备及其对水溶液中四环素去除的影响因素

以中药材三桠苦药渣和玉米秸秆为原料,分别在400、600和800℃下热解制备生物炭,并研究其对水溶液中四环素的去除及其影响因素.利用元素分析、傅里叶红外光谱(FT-IR)、比表面积分析(BET)、X射线衍射(XRD)、扫描电子显微镜(SEM)等方法对制备的生物炭进行表征;并探究热解温度、生物炭添加量、初始溶液浓度、吸附时间、溶液pH、离子强度、环境温度等因素对生物炭去除水溶液中四环素的影响;通过吸附动力学和等温吸附平衡探究两种原料制备的生物炭对溶液中四环素的吸附行为.结果表明,生物炭对四环素的吸附性能随制备温度的升高而增加,800℃制备的三桠苦药渣生物炭(EIBC800)具有最佳吸附性能.生物炭添加量、溶液pH、离子强度、吸附时间对800℃制备的三桠苦药渣生物炭(EIBC800)和玉米秸秆生物炭(CSBC800)吸附水溶液中四环素影响较大,吸附时环境温度对吸附的影响大小依赖于抗生素质量浓度.EIBC800和CSBC800对四环素的吸附行为均符合准二级动力学方程(R~2分别为0. 954 0和0. 835 5),等温吸附符合Freundlich方程(R~2分别在0. 899 1～0. 957 9和0. 973 6～0. 994 6之间),主要吸附过程为化学吸附,且吸附过程均是自发吸热的过程.通过以两种原料所制备的生物炭吸附性能对比,EIBC800吸附抗生素的能力比CSBC800更强,说明中药渣在制备生物炭去除水环境中的抗生素具有较好的应用前景.     

石家庄某制药企业污水处理过程中NH3排放研究

为了解污水处理过程中各处理单元NH₃的排放特征,采集石家庄某制药企业各污水处理单元以及经过废气治理后排放的样品,计算各采样点NH₃浓度及排放量。结果表明:各污水处理单元中,水解酸化池NH₃浓度和单位体积污水NH₃排放量均为最高,分别为62.89和3 360 mg∕m ³。各污水处理单元NH₃总排放量为0.97 kg∕h,单位体积污水NH₃排放量为9 312 mg∕m ³;经废气治理后,排入环境的NH₃为0.25 kg∕h,单位体积污水NH₃排放量为2 400 mg∕m ³,去除率为74.2%,经治理后NH₃排放量明显降低。南区、北区废气治理采用碱洗+氧化+水洗工艺,NH₃去除率分别为93.3%和83.1%;生物区废气治理采用生物滴滤床工艺,NH₃去除率为39.1%,碱洗+氧化+水洗工艺对NH₃的去除效果好于生物滴滤床工艺。