Biological Activity in a Heavily Organohalogen-Contaminated River Sediment (8 pp)

Background, Aims and Scope Sediments of the Spittelwasser creek are highly polluted with organic compounds and heavy metals due to the discharge of untreated waste waters from the industrial region of Bitterfeld-Wolfen, Germany over the course of more than one century. However, relatively few data have been published about the chloroorganic contamination of the sediment. This paper reports on the content of different (chloro)organic compounds with special emphasis on polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F), and chlorobenzenes. Existing concepts for the remediation of Spittelwasser sediment include the investigation of natural attenuation processes, which largely depend on the presence of an intact microbial food web. In order to gain more insight in terms of biological activity, we analyzed the capacity of sediment microflora to degrade organic matter by measuring the activities of extracellular hydrolytic enzymes involved in the biogeochemical cycling of carbon, nitrogen, phosphorus and sulfur. Furthermore, the detection of physiologically active bacteria in the sediment, particularly of those known for their capability to reductively dehalogenate organochlorine compounds, illustrates the potential for intrinsic bioremediation processes. Methods PCDD/F and chlorobenzenes were analyzed by gas chromatography(GC)/mass spectrometry and GC/flame ionization detection, respectively. The activities of hydrolytic enzymes were determined from freshly sampled sediment layers using 4-methylumbelliferyl (MUF) or 7-amino-4-methylcoumarin-conjugated model compounds and kinetic fluorescence measurements. Physiologically active bacteria from different sediment layers were microscopically visualized by fluorescence in situ hybridization (FISH). Specific bacteria were identified by 16S rRNA gene amplification and sequencing. Results and Discussion The PCDD/F congener profile was dominated by dibenzofurans. In addition, the presence of specific tetra and pentachlorinated dibenzofurans supported the assumption that extensive magnesium production was one possible source for the high contamination. A range of other chloroorganic compounds, including several isomers of chlorobenzenes, hexachlorocyclohexane and 1,1,1-trichloro-2,2-bis (p-chloro-phenyl)ethane (DDT), was present in the sediment. Activities of extracellular hydrolytic enzymes showed a strong decrease in those sediment layers that were characterized by high contents of absorbable organic halogen (AOX), indicating disturbed organic matter decay. Interestingly, an abnormal increase of cellulolytic enzyme activities below the organochlorine-rich layers was observed, possibly caused by residual cellulose from discharges of sulfite pulping wastes. FISH revealed physiologically active bacteria in most sediment layers from the surface down to the depth of about 60 cm, including members of Desulfitobacterium (D.) and Sulfurospirillum. The presence of D. dehalogenans was confirmed by its partial 16S rRNA gene sequence. Conclusions Results of chemical sediment analyses demonstrated high loads of organochlorine compounds, particularly of PCDD/F. Several years after stopping the waste water discharge to Spittelwasser creek, this sediment remains a main source for pollution of the downstream river system by way of the ongoing mobilization of sediment during high floods. As indicated by our enzyme activity measurements, the decomposition potential for organic matter is low in organochlorine-rich sediment layers. In contrast, the comparably higher enzyme activities in less organochlorine-polluted sediment layers as well as the presence of physiologically active bacteria suggest a considerable potential for natural attenuation. Recommendations and Perspectives From our data we strongly recommend to explore the degradative capacity of sediment microorganisms and the limits for in situ activity towards specific sediment pollutants in more detail. This will give a sound basis for the integration of bioremediation approaches into general concepts to reduce the risk that permanently radiates from this highly contaminated sediment. Submission Editor: Dr. Henner Hollert (Henner.Hollert@urz.uniheidelberg.de)     

双酚S在两种典型地带性土壤中的吸附/解吸行为研究

采用批平衡实验方法研究了双酚S（BPS）在两种典型地带性土壤中的吸附/解吸行为.结果表明,吸附动力学曲线符合拟二级动力学方程.吸附等温线呈非线性,且同时符合Freundlich和Langmuir方程.相比而言,BPS更易吸附在高有机质含量的黑土中,298 K反应温度下BPS在黑土和红壤上的最大吸附容量分别为497.8和156.6 mg·kg^-1.吸附到两种土壤中的BPS存在解吸滞后现象,这可能是由于BPS以化学吸附和微孔扩散的形式存在于土壤中的缘故.溶液pH与BPS在土壤中的吸附容量呈负相关关系,即中性形态的BPS比阴离子形态的BPS具有更高的吸附容量.与结构类似物双酚A（BPA）的吸附相比,BPS在土壤中的吸附量更低,因此具有更高的迁移能力,可能会引起更高的环境健康风险.本研究结果为了解BPS在土壤中的迁移规律提供了数据支持.     

Effects of SO2 and H2O on low-temperature NO conversion over F-V2O5-WO3/TiO2 catalysts

F-V_2 O_5-WO3/Ti02 catalysts were prepared by the impregnation method.As the content of F ions increased from 0.00 to 0.35 wt.%,the NO conversion of F-V_2 O_5-WO_3/TiO_2 catalysts initially increased and then decreased.The 0.2 F-V_2 O_5-WO_3/TiO_2 catalyst(0.2 wt.% F ion)exhibited the best denitration(De-NOx) performance,with more than 95% NO conversion in the temperature range 160-360℃,and 99.0% N2 selectivity between 110 and 280℃.The addition of an appropriate amount of F ions eroded the surface morphology of the catalyst and reduced its grain size,thus enhancing the NO conversion at low temperature as well as the sulfur and water resistance of the V_2 O_5-WO3/Ti02 catalyst.After selective catalytic reduction(SCR) reaction in a gas flow containing SO_2 and H_2 O,the number of NH3 adsorption sites,active component content,specific surface area and pore volume decreased to different degrees.Ammonium sulfate species deposited on the catalyst surface,which blocked part of the active sites and reduced the NO conversion performance of the catalyst.On-line thermal regeneration could not completely recover the catalyst activity,although it prolonged the cumulative life of the catalyst.In addition,a mechanism for the effects of S02 and H_2 O on catalyst NO conversion was proposed.     

磁性有序介孔碳的制备及其对水中双酚A的吸附

采用水热法成功制备了磁性有序介孔碳（Fe-OMC）,用于吸附水中双酚A （BPA）.采用高倍投射电镜、X射线衍射仪、傅里叶红外光谱仪、比表面积分析仪和振动样品磁强计对Fe-OMC进行表征.结果表明,该吸附剂具备较大的比表面积、独特的有序介孔孔道结构、丰富的含氧官能团以及较强的超顺磁性.Fe-OMC能够高效地吸附去除水中的BPA,平衡吸附量可达72.62mg/g,经过外加磁场分离回收后依旧具备较好的吸附性能.随着BPA浓度从1mg/L提高到20mg/L,其平衡吸附量由8.33mg/g增至91.78mg/g.随着pH值的升高呈现出先降低后升高再降低的趋势,最高吸附量出现在pH=8（75.34mg/g）.Fe-OMC对BPA的吸附过程可用准二级吸附动力学模型和Langmuir吸附等温模型进行描述.计算的热力学参数表明,Fe-OMC对BPA的吸附过程是自发进行的放热过程.     

Effects of bifenthrin on Daphnia magna during chronic toxicity test and the recovery test

IntroductionWiththedevelopmentandapplicationofnewpesticide ,insecticidehasgreatlyreducedtheharmofpesttocrops .Bifenthrinisaneffectivepyrethroidinsecticideandacaricideagainstawiderangeofinsectpests ,anditisverypoisonoustomammal,aquatic .Thisinsecticideiswi…     

锑对土壤跳虫(Folsomia candida)的毒性效应

为了解Sb（锑）对土壤无脊椎动物的毒性效应及对比不同类型土壤中Sb毒性的差异,选取死亡率、逃避率、繁殖数三组个体水平的评价指标研究了3种典型土壤（海伦黑土、祁阳红壤、北京潮土）中外源添加Sb对模式生物——跳虫（Folsomia candida）的急性毒性和慢性毒性效应.结果表明,基于实测w（Sb_总）求得的上述3种土壤中Sb影响跳虫逃避的2 d-EC₅₀（EC₅₀为半数效应浓度）分别为298、>431[高于土壤中最高w（Sb_总）]和132 mg/kg;影响跳虫死亡的7 d-LC₅₀（LC₅₀为半数致死浓度）分别为3 352、4 007、2 105 mg/kg;影响跳虫死亡的28 d-LC₅₀分别为2 271、1 865、703 mg/kg,影响跳虫繁殖的28 d-EC₅₀分别为1 799、1 323、307 mg/kg.由上述毒性阈值大小可知,跳虫逃避率的敏感性高于死亡率和繁殖数的敏感性,不同土壤中Sb对跳虫的毒性大小具有显著差异,北京潮土中Sb对跳虫的毒性与海伦黑土、祁阳红壤相比最大差别接近6倍,表明不同土壤理化性质对Sb生态毒性效应具有显著影响.但基于w（Sb_水提）求得的上述3种土壤中Sb的毒性阈值差异减小,说明水提态Sb与其毒性具有显著相关性,可以较好地解释不同土壤间Sb毒性的差异.该研究结果可为建立我国土壤中Sb的毒性预测模型及制订Sb的质量标准值提供依据.      

次氯酸钠氧化消除水中BPA的影响因素和动力学

采用常用消毒剂次氯酸钠对内分泌干扰物双酚A（BPA）的氧化消除及动力学规律进行研究,考察了加氯量、BPA初始浓度、pH值、Br^-浓度和温度各因素对降解效果的影响.结果表明,次氯酸钠对BPA的氧化降解过程符合拟一级反应动力学;pH值对该降解反应影响较大,当pH为8～9时,BPA与 HOCl的反应速率达到最大为0 .544 3　min^-1;溶液中存在Br^-会加快BPA的降解,并且其整体反应不符合拟一级动力学规律,随着Br^-浓度的增加,BPA降解得越快;温度对该降解反应的影响较大并且符合Van't Hoff规则,提高反应温度,有利于氯对BPA的降解.     

CTMAB增强调控沉积物(生物膜)吸附BPA的作用

研究了经十二烷基苯磺酸钠(SDBS]、曲拉通(TX-100)和十六烷基三甲基溴化铵(CTMAB)改性前后的沉积物(生物膜)吸附双酚A(BPA)的能力,并分析了CTMAB在沉积物(生物膜)吸附BPA过程中的增强机理及表面吸附和分配作用在总吸附中的贡献.研究结果表明,三种表面活性剂对沉积物(生物膜)吸附BPA的促进作用大小...     

Lindet ypeF(K)沸石对Zn~(2+)的吸附研究

利用粉煤灰合成Linde type F(K)沸石吸附重金属Zn2+,考察吸附剂量、pH值、反应温度对Zn 2+吸附效果影响,研究沸石吸附Zn2+的等温线与动力学,得到了相应的模型。结果表明:吸附剂量、pH值、反应温度均对Zn2+去除效果影响显著。随着吸附剂量增大,Zn 2+去除效果不断提高,饱和吸附量逐渐减小。初始pH值为3~7时,沸石对Zn2+去除率随pH值升高迅速提高。反应温度越高,沸石吸附Zn2+到达平衡时间越短。沸石对Zn2+吸附过程符合Langmuir吸附等温式,其吸附为单分子层吸附;准二级反应动力学方程能很好描述沸石对Zn2+的吸附行为。     

利用固定化技术与添加表面活性剂增强双酚A降解率的研究

以SiO_2为载体,戊二醛为交联剂,用以固定游离态漆酶降解双酚A(Bisphenol A,BPA).同时,对比了游离态漆酶与固定化漆酶在不同pH值与温度下的最佳酶活与酶稳定性,再通过添加表面活性剂来增加酶活及BPA去除效果.结果表明,与游离态漆酶相比,固定化漆酶对不同酸碱的适应性与耐热性均有所提高,在pH为2~8时,固定化漆酶的活性均高于游离态漆酶,且最佳活性温度也从游离态漆酶的40℃提高至50℃.在BPA降解率方面,固定化漆酶的降解率皆高于游离态漆酶,反应6 h后,对100 mg·L~(-1)BPA的去除率可分别达到92%与85%.通过添加非离子型表面活性剂Triton X-100,反应4 h后固定化漆酶可完全降解BPA,相对活性为67%;游离态漆酶于6 h将BPA降解完全,相对活性为32%.实验证实Triton X-100可作为酶活诱导剂用以提高漆酶活性及BPA的降解率,降低了处理成本且具有一定的应用前景.