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)     

富营养化巢湖沉积物溶解性有机质光谱时空分布特征及其环境意义

通过紫外吸收光谱（UV-vis）和三维荧光光谱（3D-EEMs）,研究典型富营养化湖泊巢湖沉积物溶解性有机质（DOM）光谱时空分布特征.结果表明,巢湖表层沉积物DOM的a（254）含量为13.1~101.7 m^-1,平均值为（32.2±16.2）m^-1.其中,夏季沉积物a（254）的含量（（46.6±25.6）m^-1）要显著高于其它季节,且湖心区a（254）平均值和变异性均小于湖滨区.表层沉积物DOM的S_275~295值从春季到冬季上随时间呈明显上升趋势.沉积物DOM荧光强度在夏季最高,在垂直剖面上总体呈下降趋势.DOM组分以酪氨酸类蛋白质和溶解性微生物产物为主,各组分在空间分布上无明显差异.巢湖沉积物DOM荧光指数（FI）为2.56~4.89,腐殖化指数（HIX）为0.57~6.78,生物源指数（BIX）为0.31~1.54.巢湖沉积物DOM主要来自于生物源,藻的生长循环会显著影响富营养化湖泊沉积物DOM的来源和性质.     

贵州草海湿地溶解性有机物的光谱特征及其与PFASs的相关性分析

为描述草海湿地DOM（dissolved organic matter,溶解性有机物）荧光特征,探究其对PFASs（per-and polyfluoroalkyl substances,全氟及多氟化合物）环境行为造成的影响,利用超高效液相色谱-质谱联用技术和三维荧光光谱技术,结合平行因子分析,开展DOM光谱学特性研究,分析ρ（DOM）与ρ（PFASs）的相关关系.结果表明:①草海湿地中共解析出3类4种荧光组分,分别为类腐殖酸[λ_Ex（360 nm）/λ_Em（450 nm）]、长波段腐殖质[λ_Ex（400 nm）/λ_Em（510 nm）]、类富里酸[λ_Ex（330 nm）/λ_Em（400 nm）]和类色氨酸[λ_Ex（280 nm）/λ_Em（350 nm）],贡献率分别为48.6%、23.6%、22.9%和4.9%,其中类腐殖质总贡献率高达72.2%.在农业生产和人类活动的影响下,总荧光强度大致呈现从入湖区向出湖区逐渐降低、湖心区略高的趋势.②在草海湿地表层水中共检出了12种PFASs,ρ（PFASs）为233.18 ng/L,每种平均值为19.43 ng/L,PFBA（perfluorobutanoic acid,全氟丁酸）是主要污染物;草海湿地入湖区点源影响特征明显,生活污水和农业生产用水是主要的潜在污染源.③相关性分析结果显示,各荧光组分含量均与ρ（PFBS）（potassium perfluorobutanesulfonate,全氟丁烷磺酸）负相关;类色氨酸含量与ρ（PFHpA）（perfluororoheptanoic acid,全氟庚酸）负相关,与ρ（PFTriDA）（perfluorotrideanoic acid,全氟十三酸）则显著正相关.研究显示,草海湿地水体腐殖化程度高,外源特征明显,共检出12种PFASs,初步揭示了草海湿地水环境中ρ（DOM）与ρ（PFASs）的相关关系,其受水体性质及化合物结构等差异的影响,有待进一步开展深入研究.      

微波消解-原子荧光法测定海洋沉积物中As的研究

研究了微波消解海洋沉积物中的As,在比较几种不同的酸消解体系后,得到适合海洋沉积物分析的酸消解体系.与传统的湿法消解比较,测试结果无显著性差异.微波消解具有快速高效、试剂用量少、空白值低、样品不易挥发等优点,已成为海洋沉积物样品前处理的有效手段.     

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 %。     

多环芳烃的同步荧光光谱技术及其对尿样中多环芳烃的鉴别

荧光光谱技术是一种灵敏度高和选择性强的光度分析方法,特别是对广泛存在于环境中的多环芳烃类化合物(PAHs)是一种有力的痕量分析手段,但在复杂混合样品的分析中却受到不同程度的限制。1971年Lloyd提出了同步激发的想法,接着Jobn,Lloyd和Dinh等分别发表了PAH类化合物同荧光光谱技术的研究报告,Dinh使用这     

氢化物发生一原子荧光光谱法测定气田废水中的痕量砷

采用氢化物发生－原子荧光光谱法测气田废水中的痕量砷。方法有取样量少，操作简单、灵敏度高、准确度高、重现性好等优点。砷的测定线性范围为1～200ng/mL，方法的检出限为0．0453ng/mL，相对标准偏差小于等于1．6％，加标回收率在96．0％～97．7％范围内。测定密码标样与气田废水中的痕量砷，获得了满意的结果。     

悬浮液进样原子荧光光谱法测定海洋沉积物样品中的痕量汞

研究了一种使用悬浮液进样原子荧光光谱法测定海洋沉积初中痕量汞的快速简便的方法。控制悬浮液的颗粒粒径在200目(d≤0.076mm)，用磁力搅拌器搅拌以保证悬浮液分散均匀稳定，以水溶液标准作标准曲线，该法方法的检出限为0．001μg/L，加标回收率为90．5％-103．4％，RSD为4．39％。将此法用于标准物质GBw07314、GBw08301、GSBZ50013—88、GSB50014—88和实验室外控样的分析，得到了满意的结果，证明该方法准确可靠。     

An investigation of methods for enriching trophoblast from maternal blood

Trophoblast deportation is known to occur in normal human pregnancy, but it is not yet clear whether these cells routinely enter the maternal peripheral circulation and are available as a source of fetal DNA for non-invasive prenatal diagnosis of genetic disorders. To resolve this issue requires an efficient method of enriching trophoblast from maternal blood combined with a means to confirm its identity. Five different techniques were tested on ten retroplacental blood samples to determine the most sensitive and operator-efficient method. Lysis of red cells alone gave the best recovery of trophoblast but had to be discounted, together with Ficoll density gradient centrifugation, due to the very low purity and the excessive time required. Fluorescence-activated cell sorting (FACS) of pre-enriched trophoblast resulted in the lowest recovery rate (8 per cent) despite a 3250-fold enrichment and a very high purity. Immunomagnetic beads (Dynabeads) coated with anti-CD 16 antibody proved to be the best method for the subsequent immunocytochemical characterization of deported trophoblast. However, IO beads coated with anti-CD45 antibody may be more useful for isolating trophoblast for prenatal diagnosis due to the high purity, enrichment (32-fold), and recovery rate (78 per cent) obtained with this method.     

Aquafluor藻细胞活体分析法在三峡库区次级河流回水区Chla测定中的校准及应用

从三峡库区次级河流大宁河、小江、汤溪河及梅溪河139m回水区中段采集水样,经实验室培养后,用丙酮萃取分光光度法和Aquafluor藻细胞活体分析法测定Chla浓度.通过对Chla萃取值(y)和活体值(x)进行回归分析,得到其回归方程为y=4.15x 2.48,t检验显示回归方程具有线性.在库区次级河流139m回水区富营养化监测中,Chla模拟值与萃取值基本吻合,相对误差＜±7%,故可以采用Chla模拟值对水体富营养化程度进行评价.