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)     

家庭中水利用装置系统的设计

结合我国家庭中水的利用现状,设计了一套具有广泛应用性的家庭中水利用装置系统,并实现了相应的自动化控制方案。同时,详细介绍了系统的设计思路与实现的主要功能,并对装置系统的有关问题进行了深入的探讨。     

BASIN SCALE WATER MANAGEMENT AND FORECASTING USING ARTIFICIAL NEURAL NETWORKS1

ABSTRACT: Water scarcity in the Sevier River Basin in south‐central Utah has led water managers to seek advanced techniques for identifying optimal forecasting and management measures. To more efficiently use the limited quantity of water in the basin, better methods for control and forecasting are imperative. Basin scale management requires advanced forecasts of the availability of water. Information about long term water availability is important for decision making in terms of how much land to plant and what crops to grow; advanced daily predictions of streamflows and hydraulic characteristics of irrigation canals are of importance for managing water delivery and reservoir releases; and hourly forecasts of flows in tributary streams to account for diurnal fluctuations are vital to more precisely meet the day‐to‐day expectations of downstream farmers. A priori streamflow information and exogenous climate data have been used to predict future streamflows and required reservoir releases at different timescales. Data on snow water equivalent, sea surface temperatures, temperature, total solar radiation, and precipitation are fused by applying artificial neural networks to enhance long term and real time basin scale water management information. This approach has not previously been used in water resources management at the basin‐scale and could be valuable to water users in semi‐arid areas to more efficiently utilize and manage scarce water resources.     

双室微生物燃料电池重金属毒性传感器的研制

构建了双室微生物燃料电池（double microbial fuel cells,DMFC）型毒性传感器分别对Cr（Ⅵ）、Cd2+、Cu2+、Zn2+进行在线检测研究。通过对反应器进行优化,确定DMFC在外电阻为1 000 Ω时达到最大功率密度;外循环速率为0.933 4 mL·min-1时反应器运行较稳定。在最优条件下,通过监测铜离子来确定检测时间为60 min,清洗时间为10 min。在以上条件下进行重金属检测,结果表明4种重金属的检测范围分别为0.3~10、0.4~10、40~160、15~80 mg·L-1。抑制率可以用来验证反应器的可行性,检测范围内抑制率与重金属浓度呈现一定的线性关系,其相关系数分别为0.959 7、0.979 5、0.944 1、0.936 6。并可得到相应的线性方程,这些方程可用于验证DMFC-传感器的稳定性。选取检测范围内的浓度进行验证,结果表明4种重金属的相对误差均小于11%,传感器相对稳定并可长期运行。     

Determination of ammonium on an integrated microchip with LED-induced fluorescence detection

A simply fabricated microfluidic device integrated with a fluorescence detection system has been developed for on-line determination of ammonium in aqueous samples. A 365-nm light-emitting diode (LED) as an excitation source and a minor band pass filter were mounted into a polydimethylsiloxane (PDMS)-based microchip for the purpose of miniaturization of the entire analytical system. The ammonium sample reacted with o-phthaldialdehyde (OPA) on-chip with sodium sulfite as reducing reagent to produce a fluorescent isoindole derivative, which can emit fluorescence signal at about 425 nm when excited at 365 nm. Effects of pH, flow rate of solutions, concentrations of OPA-reagent, phosphate and sulfite salt were investigated. The calibration curve of ammonium in the range of 0.018-1.8 μupg/mL showed a good linear relationship with R² = 0.9985, and the detection limit was (S/N = 3) 3.6 × 10^-4 μupg/mL. The relative standard deviation was 2.8% (n = 11) by calculating at 0.18 μupg/mL ammonium for repeated detection. The system was applied to determine the ammonium concentration in rain and river waters, even extent to other analytes fluorescence detection by the presented device.     

聚糖原菌富集实验及其内源过程探究

细胞衰减是微生物内源过程的一个重要组成部分,可分为由细胞死亡引起的数量衰减和由细胞活性降低引起的活性衰减两部分.通过挥发性脂肪酸（VFA）吸收速率(VFAUR)测定、荧光原位杂交技术（FISH）以及LIVE/DEAD细胞染色技术,研究了富集聚糖原菌（GAOs）在序批式反应器（SBR）系统中好氧环境下的衰减特征.结果表明,当T=30℃、进料中m(COD)∶m(P)=100时,SBR系统中GAOs富集比例达94%.测定和计算表明,SBR富集系统中GAOs衰减速率和死亡速率分别为0.132 d^-1和0.034 d^-1,其数量衰减和活性衰减占其细胞总衰减比例分别为26%和74%.可见,GAOs数量衰减只占其细胞总衰减中很小一部分,而绝大部分衰减由活性衰减所引起.     

Sulfur speciation and bioaccumulation in camphor tree leaves as atmospheric sulfur indicator analyzed by synchrotron radiation XRF and XANES

Analyzing and understanding the effects of ambient pollution on plants is getting more and more attention as a topic of environmental biology.A method based on synchrotron radiation X-ray fluorescence and X-ray absorption near edge structure spectroscopy was established to analyze the sulfur concentration and speciation in mature camphor tree leaves (CTLs),which were sampled from 5 local fields in Shanghai,China.Annual SO2 concentration,SO42-concentration in atmospheric particulate,SO42-and sulfur concentration in soil were also analyzed to explore the relationship between ambient sulfur sources and the sulfur nutrient cycling in CTLs.Total sulfur concentration in mature camphor tree leaves was 766-1704 mg/kg.The mainly detected sulfur states and their corresponding compounds were +6 (sulfate,include inorganic sulfate and organic sulfate),+5.2 (sulfonate),+2.2 (suloxides),+0.6 (thiols and thiothers),+0.2 (organic sulfides).Total sulfur concentration was strongly correlated with sulfate proportion with a linear correlation coefficient up to 0.977,which suggested that sulfur accumulated in CTLs as sulfate form.Reduced sulfur compounds (organic sulfides,thiols,thioethers,sulfoxide and sulfonate) assimilation was sufficed to meet the nutrient requirement for growth at a balanced level around 526 mg/kg.The sulfate accumulation mainly caused by atmospheric sulfur pollution such as SO2 and airborne sulfate particulate instead of soil contamination.From urban to suburb place,sulfate in mature CTLs decreased as the atmospheric sulfur pollution reduced,but a dramatic increase presented near the seashore,where the marine sulfate emission and maritime activity pollution were significant.The sulfur concentration and speciation in mature CTLs effectively represented the long-term biological accumulation of atmospheric sulfur pollution in local environment.     

辽河流域与英国中部河湖水体中溶解有机质的荧光特性

运用三维荧光光谱技术对辽河流域和英国中部水体中溶解有机质(DOM)的荧光光谱特性进行了分析.结果表明,辽河流域各研究水体中DOM包含4种荧光组分,即类色氨酸、类酪氨酸、可见光区和紫外光区类腐殖质,通过对荧光特性定量指标的分析可知,辽河流域各研究断面水体中类腐殖质物质内源作用大于陆源,DOM具有较强的新近自生源,各河流水体中DOM腐殖化程度顺序为:浑河中游海城河中游蒲河下游太子河下游.相比之下,英国河湖中,除了River Tame含有以上4种荧光组分外,其它水体中均没有发现类酪氨酸荧光物质,甚至在River Tern中仅含有类腐殖质荧光物质,河湖中DOM含有较少的新近自生源组分,以陆源影响为主.另外,辽河流域水体中类蛋白与类腐殖质荧光峰强度比值大于英国各河流水体的平均值.由此可以推断,辽河流域各研究断面大量污染物的输入,是造成其严重内源污染的主要原因,从而使水体中DOM含量增加,英国各河流断面其DOM主要来自于水体本身存在的大量微生物和浮游植物的代谢活动以及土壤有机质经雨水的冲刷流入水体的贡献.     

重金属阳离子荧光传感器合成及光谱性研究

通过亚胺缩合的反应制备出阳离子荧光传感器（Cation Fluorescent Sensors,CFSs）,并对其结构、光谱性能检测、荧光量子产率等进行了详细的研究.通过荧光化学传感器产生的荧光光谱一直是高效的分析方法,因此合成了新的基于席夫碱的荧光化学传感器,并研究了对各种金属离子的结合特性.在CH3CN溶液中测试了阳离子荧光传感器时不同阳离子的选择性响应,发现对Cu2＋有较好的选择性,可用于Cu2＋的检测.该类阳离子荧光传感器是基于2,2-联噻吩-5-乙醛的荧光发射基团和邻氨基苯甲醚为识别基团的一类阳离子荧光传感器.     

土壤溶解性有机质荧光特征及其与铜的络合能力

选取4种不同类型土壤和腐熟鸡粪,透析提取溶解性有机质(DOM),通过凝胶色谱、三维荧光光谱测定并分析了DOM的相对分子质量(M_r)分布、化学结构特征及其与铜的结合能力.结果表明,鸡粪DOM相对分子质量积分面积远高于其他样品,表现出其具有较高的有机物含量,泥炭土次之.暗棕壤、褐土和黑土较低,仅为鸡粪积分面积的4.5%~5%.鸡粪在中分子量段积分面积约占总物质的34.1%,低分子量段和高分子量段分别约占41.7%和24.2%.荧光光谱分析表明,各样品均出现类蛋白荧光峰(E_x/E_m=240~270/300~350 nm),在中、高分子量段(M_r500)暗棕壤存在的荧光峰消失.泥炭土出现了较为独特的可见光区类富里酸荧光峰(E_x/E_m=325/420 nm),该荧光峰和黑土的荧光峰在中、高分子量段(M_r500)都产生了红移现象.鸡粪分别出现了和黑土类似的紫外区类富里酸荧光峰,以及和泥炭土类似的可见光区类富里酸荧光峰,以及一类独特的类蛋白荧光峰(E_x/E_m=280/350 nm),但这种类蛋白荧光峰在中分子量段(500M_r12 000)消失.分析表明泥炭土与Cu的络合常数(lg K)为4.13,其他3种土壤与Cu的络合常数较小且差别不大,集中在2.10~3.10之间.鸡粪与Cu的结合能力最大,络合常数达到6.66.