Measurement of the pesticide methomyl by modified quartz crystal nanobalance with molecularly imprinted polymer

A simple and cost-effective analysis method based on quartz crystal nanobalance (QCN) coated with a molecularly imprinted polymer (MIP) for measurement of methomyl was investigated. In the first part of this study, a sensitive, selective and reliable quartz crystal nanobalance (QCN) sensor was designed for the selective determination of methomyl in aqueous solutions. In the second part, in order to demonstrate the applicability and performance of the fabricated sensor in the real world situation, it was successfully applied for the determination of methomyl residual in photo catalytic degradation by ZnO powders in aqueous solutions. The fabricated sensor presents a high selectivity and sensitivity (4.56 Hz per mg L^?1) for methomyl and it can be used for determination of methomyl concentration ranged between 1 to 45 mg L^?1. Furthermore, good reproducibility, R.S.D. = 2.14% (n = 5) was observed. To investigate the performance of the sensor, the change in the insecticide concentration during the photocatalytic degradation of methomyl by ZnO was investigated by QCN and UV/Vis spectroscopy. Results obtained from QCN sensor and UV/Vis spectroscopy measurement are in good mutual agreement. So the fabricated sensor may provide an efficient, low cost, easy-to-use method for the in-field evaluation of specific targeted analytes in aqueous solutions which in turn may lead to improved food and water safety.     

石油降解菌的分离鉴定及4株芽胞杆菌种间效应

通过富集培养和分离纯化的方法,从天津大港油田石油污染土壤和渤海海上钻井平台洗油污水中分离出6株石油降解细菌,生理生化试验及16S r DNA序列分析鉴定表明,它们分别属于Bacillus芽胞杆菌属(S1、S2、S3、S4)、Pseudomonas假单胞菌属(W1)和Ochrobactrum苍白杆菌属(W2),其中,S3具有最高的烷烃(41.3%)和芳烃(30.9%)降解率,从石油污染场地中筛选出的内源微生物对本油田石油的降解效果优于外源物种.对4株芽胞杆菌属菌株构建微生物组进行石油降解实验,结果表明,由S1和S4构成的微生物组F3具有最高的烷烃(50.5%)和芳烃(54.0%)降解率,比单菌降解率分别提高了69.9%和156.1%,同时比最优降解单菌S3的降解率分别高出22.1%和74.6%,而由S2和S3构成的微生物组F4对烷烃和芳烃的降解率最低,分别为18.5%和18.9%,比单菌降解率降低了55.3%和39.0%,实验表明同菌属微生物种间对石油的降解同时存在协同促进和拮抗抑制作用,芽胞杆菌属内亲缘性近的菌株之间对石油降解主要表现为促进作用.     

碱活化过一硫酸盐降解水中环丙沙星

采用碱活化过一硫酸盐(peroxymonosulfate,PMS)对环丙沙星(ciprofloxacin,CIP)的去除进行了系统地研究.结果表明,碱活化PMS体系能够高效地去除CIP.通过自由基捕获实验确定了单线态氧(~1O_2)和超氧自由基(O_2~-·)是反应体系中的主要活性物种.NaOH浓度、PMS浓度、反应温度和共存阴离子等对CIP在碱活化PMS体系中的去除均有一定影响.随着NaOH和PMS浓度的增加,CIP的降解均呈现出先增加后降低的趋势.提高反应温度能够加大CIP的反应速率,经过阿伦尼乌斯方程拟合得到的反应活化能为5.09 k J·mol~(-1).不同的阴离子对CIP的去除呈现不同的影响:Cl~-、SO_4~(2-)和NO_3~-对CIP的降解没有呈现明显的作用,H_2PO_4~(2-)能够有效地抑制环丙沙星的去除,而CO_3~(2-)极大地促进了反应进程.通过UPLC-MS/MS可检测到10种降解产物,CIP分子结构中的哌嗪环易于受到活性物种的攻击.     

β-In2S3的制备及其太阳光下降解土霉素

利用水热反应法制备β-In2S3纳米颗粒光催化剂,并利用SEM、TEM和XRD等对其进行分析表征;采用土霉素溶液模拟四环素类抗生素废水,探讨In2S3对土霉素的降解效果.结果表明,β-In2S3为立方相纳米颗粒结构,该纳米颗粒由纳米片组成,直径约15~30 nm.以太阳光为辐射光源,In2S3对土霉素具有良好的光催化降解效果,在4 h内对初始浓度为30 mg·L-1的土霉素降解率可达98%以上.降解土霉素后的催化剂在无水乙醇中清洗并烘干,经4次循环利用后,β-In2S3的降解能力仍能达到85%以上,表明β-In2S3光催化剂具有良好的稳定性以及光催化活性.     

原始红松林退化演替后土壤微生物功能多样性的变化

为了全面了解原始红松林退化演替为次生林后土壤生境及土壤微生物功能多样性的变化规律,以小兴安岭典型的原始阔叶红松林、退化演替后先锋阶段的白桦林及亚顶级阶段的硬阔叶林为研究对象,采用Biolog-ECO微平板检测法,分析三者0~ < 10 cm和10~20 cm表层土的土壤微生物功能多样性变化规律.结果表明:各林型土壤微生物的AWCD值（平均颜色变化率）随培养时间的延长而增加,培养初期表现为原始阔叶红松林>硬阔叶林>白桦林;培养末期表现为原始阔叶红松林>白桦林>硬阔叶林,三者的AWCD值在0~ < 10 cm土层分别为1.06、0.86、0.81,10~20 cm土层分别为0.68、0.47、0.45,原始林显著高于次生林（P < 0.05）,说明原始林土壤微生物对单一碳源的代谢活性显著高于次生林;同一林型下土壤微生物的AWCD值均表现为0~ < 10 cm土层显著高于10~20 cm土层（P < 0.05）. Shannon-Wiener多样性指数、Simpson指数、McIntosh指数和Richness丰富度指数也均表现为原始林显著高于次生林（P < 0.05）.原始林土壤微生物对各类碳源的综合利用强度均大于次生林,不同林型下土壤微生物群落的优势碳源类型存在一定的差异,碳水类、氨基酸类、羧酸类和多聚物类碳源是原始林退化演替后土壤微生物群落在碳源利用上发生变化的敏感碳源.      

In-situ synthesis of TiO2 rutile/anatase heterostructure by DC magnetron sputtering at room temperature and thickness effect of outermost rutile layer on photocatalysis

TiO_2 rutile/anatase heterostructure thin films with varying rutile thickness have been in-situ synthesized via DC magnetron sputtering with Ar gas at room temperature. The crystal texture, surface morphology, energy gap and optical properties of the films have been investigated by X-ray diffraction meter, grazing incidence X-ray diffraction meter, Raman spectroscopy, scanning electron microscopy, and UV–visible spectrophotometer, which indicates that the rutile/anatase heterostructure films are successfully fabricated. The further degradation experiments display that the photocatalytic activity can be dramatically affected by the thickness of the outmost rutile layer and the 100 nm thickness exhibits the best performance in all of the TiO_2 thin films. With the increase of the outmost rutile layer, the optical band gap of TiO_2 film displays a systematic decrease slightly. However,the change in photocatalytic activity does not coincide with that in the band gap. The photoresponse and electrochemical properties of the thin films have been characterized to understand the mechanism of the varied photocatalytic activity.     

Pd-MnO2 nanoparticles/TiO2 nanotube arrays (NTAs) photo-electrodes photo-catalytic properties and their ability of degrading Rhodamine B under visible light

Pd-MnO_2/TiO_2 nanotube arrays(NTAs) photo-electrodes were successfully fabricated via anodization and electro deposition subsequently; the obtained Pd-MnO_2/TiO_2 NTAs photo electrodes were analyzed by scanning electron microscopy(SEM), X-ray diffraction(XRD) and characterized accordingly. Moreover, the light harvesting and absorption properties were investigated via ultraviolet–visible diffuse reflectance spectrum(DRS); photo degradation efficiency was investigated via analyzing the photo catalytic degradation of Rhodamine B under visible illumination(xenon light). The performed analyses illustrated that Pd-MnO_2 codoped particles were successfully deposited onto the surface of the TiO_2 nanotube arrays;DRS results showed significant improvement in visible light absorption which was between400 and 700 nm. Finally, the photo catalytic degradation efficiency results of the designated organic pollutant(Rhodamine B) illustrated a superior photocatalytic(PC) efficiency of approximately 95% compared to the bare TiO_2 NTAs, which only exhibited a photo catalytic degradation efficiency of approximately 61%, thus it indicated the significant enhancement of the light absorption properties of fabricated photo electrodes and their yield of UOH radicals.     

流体剪切与超声空化破解剩余污泥的参数优化

为提高剩余污泥的破解效果并降低能耗,采用FS（fluid shear,流体剪切）、UC（ultrasonic cavitation,超声空化）、FS和UC联合工艺（FS-UC,UC-FS）破解剩余污泥,并应用单因素试验结合响应面法对联合工艺进行优化.结果表明:FS对剩余污泥破解效果一般,只在开始阶段具有较好效果,随作用时间延长,破解效果未有显著提高甚至下降.UC对剩余污泥破解效果明显,随作用时间延长,破解效果显著提升,但能耗也随之增大,EDR（energy disintegration ratio,效能比）明显下降.相同作用时间下,UC破解效果优于FS破解效果,UC破解剩余污泥的DD_COD（degree of disintegration,破解率）与EDR均明显高于FS方法.单因素试验得出的较优FS作用时间范围为2~8 min,较优UC作用时间范围为5~15 min.响应面法试验结果显示,联合工艺的剩余污泥破解效果和能量利用率均优于单一方法,联合工艺中FS-UC工艺的破解效果优于UC-FS工艺.FS-UC工艺的最佳参数:FS处理5.6 min再UC处理15.0 min,该条件下剩余污泥实际DD_COD为50.8%,EDR为26.8%.UC-FS工艺的最佳参数:先UC作用15.0 min再FS作用7.8 min,该条件下剩余污泥实际DD_COD为36.5%,EDR为17.1%.研究显示,以DD_COD和EDR为指标,4种工艺的高效性顺序为FS-UC > UC-FS > UC > FS,其中FS-UC工艺具有能耗低、破解效率高的特点,是4种工艺中剩余污泥破解效果最好的一种工艺.      

河北平原潮土中微生物对氮降解特征

了解土壤中微生物对氮素降解规律,对于土壤氮污染修复具有重要现实意义.从河北平原潮土中筛选出8种高效氨化细菌、硝化细菌、异养硝化好氧反硝化细菌,对所筛菌种进行16S r DNA分析,选出最适菌株通过固定化载体将菌种制成菌剂.探讨了用加入所筛菌种及拮抗菌的菌液和地表水分别滴灌小白菜对土壤中的氮降解产生的影响,并测定土样磷脂脂肪酸(PLFA)的值.结果表明:以硅藻土为载体硝化细菌的氨氮降解率达到38%,硝态氮合成率为205%;以硅藻土为载体的氨化细菌氨氮合成率为1 711%,异养硝化好氧反硝化细菌的硝态氮降解率达到367%.加所筛菌液滴灌对土壤总氮和氨氮的降解效果较好,硝化作用也较强,加菌后土壤中微生物量明显增加,且更快到达峰值.对不同土样不同时间磷脂脂肪酸数据分析发现,在白菜生长过程中,土壤中的微生物含量均产生了1次峰值,且加入所筛菌的先到达峰值.对于任丘和阜城土样来说,加入所筛菌后,土壤中微生物种类相应增多,对土壤微生物环境有所改善,微生物也比较活跃.     

道路灰尘中有机磷阻燃剂污染特征及人体暴露

利用气质联用仪(GC-MS)定量分析了苏州市25个道路灰尘样品中4种有机磷阻燃剂(organophosphate flame retardants,OPFRs)的含量水平和分布特征,并估算了成人、儿童和环卫工人灰尘摄入和呼吸暴露两种不同途径的日暴露量.结果表明,在灰尘样品中4种OPFRs均有不同程度检出,总OPFRs的含量范围为ND~8 901.66 ng·g~(-1),中位值为1 039.21 ng·g~(-1).三(1-氯-2-丙基)磷酸酯[Tris(1-chloro-2-propyl)phosphate,TCPP]、磷酸三(丁氧基乙基)酯[Tris(2-butoxyethyl)phosphate,TBEP]、磷酸三(1,3-二氯-2-丙基)酯[Tris(1,3-dichloro-2-propyl)phosphate,TDCPP]和磷酸三(2-氯乙基)酯[Tris(2-chloroethyl)phosphate,TCEP]含量范围分别为0~6 931.46、0~2 021.15、0~788.44和0~62.16 ng·g~(-1).在高暴露情景下,成人、儿童和环卫工人通过摄入灰尘暴露ΣOPFRs的日均暴露量分别是125.68、915.78和6 314.16 pg·kg~(-1),儿童的暴露量比普通成人高6倍;而成人、儿童和环卫工人通过呼吸途径暴露ΣOPFRs的日均暴露量分别为3.07E-02、1.89E-02和1.54E-01 pg·kg~(-1).因此灰尘中OPFRs对于儿童和环卫工人的潜在危害更大.