氮硫共掺杂生物炭活化过硫酸盐去除地下水中难降解有机污染物的效能研究

针对水环境中2,4--二氯酚(2,4--DCP)污染,笔者以水稻秸秆为生物炭前驱体,硫脲为双原子掺杂剂,通过高温热解工艺制备了高效吸附和催化性能的氮硫共掺杂生物炭(NSBC),用于活化过一硫酸盐(PMS)降解2,4--DCP,并对其进行表征。结果表明,双原子掺杂显著提高了生物炭材料的比表面积、氧化还原活性和活性位点,如含氧官能团和氮、硫官能团。在最佳条件下,NSBC具有高效的催化能力,5 min内2,4--DCP的降解率为95.30%。NSBC/PMS体系(0.542 min^-1)的降解速率常数是BC/PMS体系(0.197 min^-1)的2.7倍。此外,在较宽的pH值范围内NSBC仍具有较好的催化性能。电子自旋共振和猝灭实验分析表明,活化PMS生成的¹O₂和·O^-₂作为2,4--DCP的降解过程的主要活性氧物种(ROS)。     

苜蓿基生物炭催化硫化物还原处理顺-二氯乙烯

顺-二氯乙烯(Cis-DCE)是高氯代烯烃在不完全降解过程中产生的毒性更强的中间产物。为了将Cis-DCE彻底地无毒化处理,本文提出了一种使用苜蓿基生物炭催化硫化物还原处理Cis-DCE的新技术。结果表明：3种苜蓿基生物炭(MXBC-400、MXBC-600和MXBC-800)对Cis-DCE均具有一定的吸附效果,但只有MXBC-600和MXBC-800可以催化硫化物,还原脱氯Cis-DCE,其中MXBC-800的催化性能最佳,可以将反应体系中的Cis-DCE几乎完全降解为乙炔,反应结束时乙炔与Cis-DCE的物质的量之比约为0.998 7∶1;材料投加量、硫化物(Na₂S)浓度、pH和反应温度的增加都会促使Cis-DCE降解效率的提升,对初始浓度在5.0～20.0 mg/L范围内的Cis-DCE去除率都能达到90%以上;Cis-DCE的降解机制主要是β消除反应,其降解途径为Cis-DCE→氯乙炔→乙炔;较大的比表面积、材料表面丰富的碳氧及含氮官能团是材料催化能力的关键因素;MXBC-800具有良好的催化稳定性。     

响应曲面法优化生物质炭去除水溶液中的阿特拉津

将农业废弃物大豆秆在450℃缺氧条件下热裂解制备生物质炭。采用元素分析仪、扫描电镜(SEM)、傅里叶变换红外光谱(FTIR)、光电子能谱分析(XPS)等手段对生物质炭进行理化性质分析;应用响应曲面法(RSM)下的中心合成设计(CCD)功能研究4个因素(初始pH、吸附剂质量浓度、阿特拉津质量浓度、温度)对阿特拉津去除率的影响;建立二阶模型,并通过方差分析验证二阶方程的有效性。结果表明:生物质炭表面充满孔状结构,且富含C=C、C-C、CHx、-C-OR、-COOR等官能团;吸附阿特拉津后生物质炭在羟基(-OH)的位置产生了新的吸收峰,推测羟基官能团在吸附过程中发挥了重要作用。RSM法优化最佳吸附去除阿特拉津条件为:初始阿特拉津质量浓度为5mg/L、pH=6.67,吸附剂质量浓度为7.75g/L、温度为32℃;在该条件下阿特拉津的吸附去除率达到92.18%。该研究可为评价施加生物质炭土壤中阿特拉津的迁移规律及阿特拉津污染水体修复提供参考。     

生物炭对磷石膏中磷的固化作用

磷石膏中的磷在雨水淋滤作用下浸出,将污染堆场附近水体。本研究采用生物炭固化磷石膏中的磷,以减少其对周遭水体的污染。主要通过模拟固化实验和对照浸出实验,分析生物炭用量、反应时间和温度、初始pH值对固化效果的影响,通过XRD、SEM-EDS分析固化后的生成物。实验结果显示,在生物炭用量为25 mg时,单位固化量达到最大值13.20 mg/g;在反应温度T=293 K、初始pH=7条件下,反应平衡时间72 h时浸出液的磷平衡浓度C_e= 1.40 mg/L;温度提升有助于提高生物炭的固化效果,当T=308 K时,浸出液的磷平衡浓度C_e=0.167 mg/L;碱性条件有利于固化反应持续进行,在pH=11条件下,浸出液的磷平衡浓度C_e=0.153 mg/L。实验结果表明生物炭对磷石膏中的磷具有明显的固化效果。磷石膏中的二水硫酸钙溶解后,Ca²⁺与表面带负电的生物炭结合,在生物炭显微结构的凹陷处,化学吸附溶液中的磷酸根生成了絮状、团簇状的羟基磷灰石(HAP)沉淀,从而使浸出磷得到有效控制。     

生物质炭负载纳米零价铁对水中硝态氮的还原去除机理研究

采用液相还原法成功制备纳米零价铁,并组装出生物质炭负载纳米零价铁复合材料(NZVI/BC)。XRD图谱显示,NZVI/BC由生物质炭(BC)和纳米零价铁(NZVI)两种成分复合而成;SEM图像显示,加入生物质炭之后,NZVI颗粒在炭表面分散良好。研究考察溶液p H值、还原剂投加量、铁/炭比和NO-3初始浓度等因素对NZVI/BC还原性能的影响。结果表明,NZVI/BC显示出优良的还原性能。在相同条件下,反应2 h,NZVI对NO-3的去除率为75%,而NZVI/BC对NO-3的去除率为96%。NZVI/BC是一种具有应用前景的硝态氮净化材料。     

热活化过硫酸盐降解氧氟沙星特性及响应面优化

为了探究热活化过硫酸盐（PS）技术对水中氧氟沙星（OFX）的氧化降解作用,考察了反应温度、体系的初始pH、PS的初始浓度、OFX的初始浓度对OFX降解效果的影响;并在单因素实验的基础上,选取反应时间、体系的初始pH、PS的初始浓度和OFX的初始浓度4个因素进行了响应面优化实验。结果表明：最佳降解条件为,反应温度60℃、PS初始浓度4.0 mmol/L、pH=4.7、OFX初始浓度0.03 mmol/L、反应时间60 min,此时OFX的降解率为81.29%;4个因素对热活化PS降解OFX均有影响,其影响显著性从大到小为反应时间、OFX的初始浓度、PS的初始浓度、初始pH。利用响应曲面法模拟出反应体系的最佳条件,经实验验证,OFX降解率为93.78%,与预测最佳结果95.00%基本相符,表明模型可靠有效。     

煤层产甲烷菌对胍胶的生物降解实验

胍胶压裂液的低温破胶问题事关煤层的增透效果,为探讨产甲烷菌群对胍胶生物降解的影响,以内蒙古某矿褐煤样品为研究对象,以富集的新鲜矿井水为菌源,配比不同浓度的胍胶与煤的混合液,开展生物甲烷代谢实验。以产气总量、CH₄含量、胍胶分子官能团和C、H元素含量变化以及液相产物等指标表征煤层产甲烷菌群对胍胶的生物降解特性。实验结果表明:加入胍胶能提高煤制生物气产量,代谢后体系溶液黏度明显降低;降解后胍胶大分子中C、H元素的含量明显下降,胍胶的表面粗糙度增加;胍胶降解后主要特征峰表现为-OH基团及C-O基团的含量减少,甲基官能团振动吸收峰消失;生物降解溶液中葡萄糖醛酸含量增加。实验验证了煤层产甲烷菌对胍胶的降解作用及效果,为胍胶压裂液的低温破胶技术提供了有力依据。      

共存重金属离子对针铁矿活化过硫酸盐去除水中磺胺吡啶的影响

基于硫酸根自由基的高级氧化技术能有效降解水中磺胺类药物残留。由于在自然环境中共存重金属会对环境修复效果产生一定影响,文中重点研究了不同pH环境条件下不同重金属离子对针铁矿活化过硫酸盐(PS)去除水中磺胺吡啶(SPY)的影响。不同类型重金属离子(Cu^2+、Pb^2+、Cd^2+,0.2mmol/L)在反应体系(初始条件:针铁矿,1.0g/L;PS,4mmol/L;SPY,10mg/L;pH=8.2)中对SPY的降解对比研究发现:在无重金属共存的条件下,针铁矿/PS体系降解SPY的去除率为25.2%;Pb^2+和Cd^2+对针铁矿/PS体系的影响较弱,去除率分别为30.8%和34.8%;Cu^2+的促进作用很大,可以使SPY被完全降解(100%)。机理分析认为,在针铁矿/PS体系中Pb^2+和Cd^2+主要通过影响吸附作用导致磺胺吡啶被去除,而Cu^2+主要通过自身活化PS的作用。不同pH条件(3.0,8.0,12.0)实验证实弱碱性条件下,Cu^2+/针铁矿/PS能够发挥较高的活性从而降解SPY。本文结果为采用针铁矿活化过硫酸盐技术修复类似复合污染地下水环境提供了实验依据。     

Fe(Ⅱ)/针铁矿复合系统对水中橙黄G的吸附-还原脱色研究

系统研究了Fe(Ⅱ)/针铁矿复合系统对偶氮染料橙黄G(简称OG)的吸附-还原脱色机理,重点考察了反应条件p H值、Fe(Ⅱ)与OG摩尔比对OG还原脱色效果的影响。研究结果表明,矿物表面结合态Fe(Ⅱ)能够有效提高还原脱色反应速率;OG脱色反应非常符合准一级反应动力学方程,速率常数(k)随p H值的升高、亚铁离子吸附量的增加而显著增大;当OG初始浓度为50 mg/L、Fe(Ⅱ)与OG的摩尔比为27.0时,Fe(Ⅱ)/针铁矿复合系统对OG的去除脱色率在弱碱性条件下1 h内可达到100%。该系统对OG去除脱色的高效性是界面吸附与还原协同作用的结果。该研究可为有效应用Fe(Ⅱ)/针铁矿复合系统在缺氧环境中的污染修复提供理论指导。     

季铵盐插层氧化石墨的分子模拟

<正>氧化石墨(graphite oxide,GO)是一种层状结构的碳氧化合物,其结构层上的含氧官能团以羟基(-OH)和环氧基(C-O-C)为主,仅在结构层边缘接有少量的羧基(-COOH)和羰基(-C=O)等,这些官能团使GO的结构层表面在水溶液或碱水溶液中带负电,可以通过离子键作用(离子吸附)将阳离子型表面活性剂插入到GO层间,电荷平衡后,进而通过疏水键作用(分子吸附)将有机分子插入GO层间,制得的插层复合物表现出良好的力学、热力学、阻燃、光电、催化等性能,在导电、吸附、耐高温、环保、功能膜和生物传感器等众多领域具有广泛的应用。其中,以GO为前驱体,将季铵盐(CnTAB)分子插     

The terrestrial fauna of the Late Triassic Pant-y-ffynnon Quarry fissures,South Wales,UK and a new species of Clevosaurus (Lepidosauria: Rhynchocephalia)

Pant-y-ffynnon Quarry in South Wales yielded a rich cache of fossils in the early 1950s, including articulated specimens of new species (the small sauropodomorph dinosaur Pantydraco caducus and the crocodylomorph Terrestrisuchus gracilis), but no substantial study of the wider fauna of the Pant-y-ffynnon fissure systems has been published. Here, our overview of existing specimens, a few described but mostly undescribed, as well as freshly processed material, provides a comprehensive picture of the Pant-y-ffynnon palaeo-island of the Late Triassic. This was an island with a relatively impoverished fauna dominated by small clevosaurs (rhynchocephalians), including a new species, Clevosaurus cambrica, described here from a partially articulated specimen and isolated bones. The new species has a dental morphology that is intermediate between the Late Triassic Clevosaurus hudsoni, from Cromhall Quarry to the east, and the younger C. convallis from Pant Quarry to the west, suggesting adaptive radiation of clevosaurs in the palaeo-archipelago. The larger reptiles on the palaeo-island do not exceed 1.5?m in length, including a small carnivorous crocodylomorph, Terrestrisuchus, and a possible example of insular dwarfism in the basal dinosaur Pantydraco.     

The effect of water on accessory phase solubility in subaluminous and peralkaline granitic melts

The solubilities of columbite, tantalite, wolframite, rutile, zircon and hafnon were determined as a function of the water contents in peralkaline and subaluminous granite melts. All experiments were conducted at 1035 °C and 2 kbar and the water contents of the melts ranged from nominally dry to approximately 6 wt.% H₂O. Accessory phase solubilities are not affected by the water content of the peralkaline melt. By contrast, solubilities are affected by the water content of the subaluminous melt, where the solubilities of all the accessory phases examined increase with the water content of the melt, up to 2 wt.% H₂O. At higher water contents, solubilities are nearly constant. It can be concluded that water is not an important control of accessory phase solubility, although the water content will affect diffusivities of components in the melt, thus whether or not accessory phases will be present as restite material. The solubility behaviour in the subaluminous and peralkaline melts supports previous spectroscopic studies, which have observed differences in the coordination of high field strength elements in dry vs. wet subaluminous granitic glasses, but not for peralkaline granitic glasses. Lastly, the fact that wolframite solubility increases with increasing water content in the subaluminous melt suggests that tungsten dissolved as a hexavalent species.     

Quaternary stresses revealed by calcite twinning inversion: insights from observations in the Savonnières underground quarry (eastern France)

Calcite samples were extracted both from the rock matrix and the superficial coating of a karstified fault plane of an underground quarry, located in the eastern border of the Paris basin. The karstification is dated as Quaternary. Analysis of mechanical calcite twinning reveals that only the calcite matrix has also undergone a compression trending WNW that can be attributed to the Mio-Pliocene alpine collision. Both coating and matrix have undergone a strike-slip regime with σ₁ roughly trending north–south, that could correspond to the regional present-day state of stress, a strike-slip compression rather trending NNW, modified by local phenomena. To cite this article: M. Rocher et al., C. R. Geoscience 335 (2003).     

HYDROGEOLOGY

正20141756 Chen Ruige(Mathematical College,China University of Geosciences,Beijing100083,China);Zhou Xun Numerical Simulation of Groundwater Level Fluctuation in a Coastal Confined Aquifer with Sloping Initial Groundwater Level Induced by the Tide(Geological Bulletin of China,ISSN1671-2552,CN11-4648/P,32(7),2013,p.1099-1104,6 illus.,16 refs.) Key words:confined water,groundwater level     

METAMORPHIC PETROLOGY

正20141408 Cai Jia(Institute of Geology,Chinese Academy of Geological Sciences,Beijing100037,China);Liu Fulai Petrogenesis and Metamorphic P-T Conditions of Garnet-Spinel-Biotitebearing Paragneiss in Danangou Area,Daqingshan-Wulashan Metamorphic Complex Belt(Acta Petrologica Sinica,ISSN1000-0569,CN11-1922/P,29(7),     

SERIALS

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GEOPHYSICAL EXPLORATION

正20142386An Guoying(China Aero Geophysical Survey and Remote Sensing Center for Land and Resources,Beijing 100083,China)Application of Satellite Remote Sensing in Regional Hydrogeological Investigation:Taking Cenozoic Strata in Wenquan Sheet(1∶250 000)of Karakoram Range as an Example(Geosci-     

QUATERNARY GEOLOGY & GEOMORPHOLOGY

正20141016An Chengbang(Key Laboratory of Western China’s Environmental Systems,Ministry of Education,Lanzhou University,Lanzhou 730000,China);Zhao Yongtao Lake Records during the Last Glacial Maximum from Xinjiang,NW China and Their Climatic Impli-     

PETROLEUM GEOLOGY

正20141538 Cao Qing(School of Earth Sciences and Engineering,Xi’an Petroleum University,Xi’an 710065,China);Zhao Jingzhou Characteristics and Significance of Fluid Inclusions from Majiagou Formation,Yichuan Huangling Area,Ordos Basin(Advances in Earth Science,ISSN1001-8166,CN62-1091/P,28(7),2013,p.819-828,7 illus.,3 tables,43 refs.)     

GEOCHEMISTRY

正20142002 Wei Hualing(Institute of Geophysical and Geochemical Exploration,Chinese Academy of Geological Sciences,Langfang065000,China);Zhou Guohua Element Content and Mineral Compositions in Different Sizes of Soil in Tongling Area,Anhui Province(Geological Bulletin of China,ISSN1671-2552,CN11-4648/P,32(11),2013,p.1861