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)     

酒石酸钾钠(PST)对纳滤处理重金属废水的强化机理

在已有纳滤处理重金属实验中,发现适当添加酒石酸钾钠可以使金属去除率增大的同时膜通量没有明显降低,而且纳滤膜表面接触角与膜通量呈稳定的负线性关系。采用X-射线（单晶）衍射法对酒石酸钾钠（PST）与Cd2+、Ni2+、Zn2+、Cu2+ 4种金属离子的络合配位方式进行分析。通过对晶体结构和键长键角等参数的分析表明,酒石酸钾钠主要通过羧基氧原子和邻位羟基氧原子与金属离子鳌合配位形成五元鳌合环;络合配位的中心金属离子Ni2+、Zn2+和Cu2+是六配位形式,而Cd2+是七配位形式。进一步通过配位分析方法计算了不同配比下配合物水分子量的大小,发现其变化特征与纳滤膜通量的变化趋势相似;金属离子络合物体积变化受到配位键长键角和酒石酸根配位数的控制,其变化特征与纳滤截留率变化一致。说明络合物的配位水分子量和配位体积大小2个参数能够分别解释PST强化纳滤处理重金属膜通量和截留率的变化特征。     

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.     

流动注射在线氢化物发生—原子荧光光谱法测定环境水样中痕量无机汞和有机汞

提出了一种流动注射在线氢化物发生—原子荧光光谱法测定水样中痕量无机汞和有机汞的分析方法。以溴化剂作为有机汞的消解剂 ,在有、无溴化剂的存在下 ,采用流动注射在线氢化物发生—原子荧光光谱法分别测定总汞和无机汞 ,差减法求出有机汞的含量。方法操作简便快速 ,灵敏度高 ,干扰少 ,经加标回收实验验证 ,回收率达 95 %～ 10 5 %。     

典型可溶有机质与磺胺二甲嘧啶的络合作用研究

以藻源有机质(AOM)和腐殖酸(HA)作为典型生物大分子可溶有机质(DOM)和腐殖化DOM,采用荧光猝灭滴定和光谱分析考察磺胺二甲嘧啶(SMZ)与DOM的络合作用.三维荧光光谱结合平行因子分析显示AOM荧光组分主要由类酪氨酸和类色氨酸物质组成,而类富里酸和类腐殖酸物质是HA荧光组分的主要构成.4种荧光组分可与SMZ发生不同程度的静态猝灭,且猝灭过程中DOM分子构象改变.同步荧光光谱结合二维相关图谱进一步发现类酪氨酸优先于类色氨酸组分与SMZ发生络合作用.Ryan-Weber非线性模拟拟合表明AOM中各荧光组分与SMZ的络合稳定常数(logK)大小为:类富里酸(3.33)类酪氨酸(3.12)类色氨酸(2.15)类腐殖酸(1.57);而HA中大小为:类富里酸(3.06)类腐殖酸(2.02).总体上生物大分子DOM对SMZ的亲和力高于腐殖化DOM.DOM与SMZ的相互作用可改变水环境中抗生素的形态和归趋,影响其生物有效性和生态毒性.     

北京森林土壤富里酸亚组分的表征及荧光指标分析

为探究土壤FA（富里酸）的结构组成及其腐殖化和芳香性特征,采用SFS（同步荧光光谱）技术结合FRI（荧光区域积分）、DSFS（导数荧光光谱）及PCA（主成分分析）对土壤FA亚组分的荧光光谱特征及荧光指标间的相关性进行了分析.利用XAD-8吸附树脂结合初始pH为3、5、7、9和13的Na₄P₂O₇（焦磷酸钠）缓冲溶液逐步洗脱技术将土壤FA分别分级得5种亚组分（FA₃、FA₅、FA₇、FA₉和FA₁₃）.结果表明:①FA₃-FA₁₃的SFS体现3类荧光峰,分别代表类蛋白、类富里酸和类腐殖酸物质.FA₃和FA₅含有含量相近的类蛋白、类富里酸和类腐殖酸物质,而FA₇-FA₁₃含有的主要成分是类蛋白物质;同时,FA₇-FA₁₃的类富里酸和类腐殖酸较FA₃和FA₅更为复杂,且FA₇-FA₁₃含有更多易降解的单环芳香族化合物.②FA₃和FA₅的类酪氨酸和类色氨酸物质被识别,且FA₇-FA₁₃的类色氨酸含量明显大于类富里酸和类腐殖酸含量.③FA₃-FA₁₃光谱荧光强度指标（I₂₄₀/I₃₄₀、I₂₄₀/I₄₅₀、I₃₄₀/I₂₇₀、I₄₅₀/I₂₇₀和I₄₅₀/I₃₄₀）的对比分析表明,FA₃和FA₅的腐殖化程度和芳香性均大于FA₇-FA₁₃.④荧光指标A_FLR/A、A_HLR/A、S_270-340、S_270-450、A₂/A₁和A₃/A₁可作为指示亚组分芳香性的优化指标,且A_HLR/A、A₂/A₁和A₃/A₁可作为最佳指标反映亚组分的腐殖化程度.研究显示,土壤FA亚组分的结构表征及荧光指标分析为后续FA亚组分与环境污染物相互机理研究提供依据,为探究有机质的结构特性和环境行为提供理论支撑.      

太湖北部湖区春、冬季节天然有机质的荧光特征及环境意义

天然有机质(OM)广泛存在于各类水体,含有丰富的碳、氮、磷等生源要素,其形成、转化、归宿及其相伴随的营养盐再生过程是水生态系统营养盐生物地球化学循环的重要环节,在湖泊蓝藻水华暴发过程中势必也扮演着非常重要的营养盐供给者的角色.本研究于2015年2月和5月分别在太湖北部湖区采集了17个样品,利用POM-DOM PARAFAC三维荧光模型解析春、冬季节颗粒态有机质(POM)和溶解态有机质(DOM)的荧光特征及来源,并探讨POM和DOM各荧光组分之间及其与叶绿素a(Chla)的关系.结果表明,春、冬季节太湖北部湖区POM和DOM的荧光峰、荧光中心位置和荧光强度均存在明显的差别;POM有着比DOM更复杂的组分构成.综合POM和DOM的荧光强度和荧光指数可知,春、冬季节太湖北部湖区POM和DOM均以自生源为主,河口区受陆源贡献较大.POM(C1p~C5p)和DOM(C1d~C5d)有5种荧光组分,分别是类色氨酸(C1和C2)、类腐殖质(C3和C4)及类酪氨酸(C5).POM和DOM的荧光组分特征存在明显的差别;春、冬季节POM均以类腐殖质荧光C3为主,荧光组分高值区分别集中在梅梁湾区域和湖心区;而DOM均以类蛋白组分C2、C1和C5为主,荧光组分高值区均分布在竺山湾区域.相关分析结果显示,春季C1d与C2d(P0.01)、C3d与C4d(P0.01)、C1p与C4p(P0.05)、C2p与C5p(P0.01)均具有较强的相关性.值得注意的是,C3d(P0.01)、C4d(P0.05)与C3p均具有较好的相关关系,表明POM与DOM在组分、来源上具有某种联系.与春季类似,冬季荧光组分C1d与C2d、C3d与C4d、C1p与C2p、C1d与C2p亦具有极好的相关性(P0.01).春季C5d与Chla之间存在正相关关系(P0.01),而C2d(P0.05)、C3p(P0.01)与Chla之间具有负相关关系;冬季C4d与Chla之间也存在负相关关系(P0.05).