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)     

面向新世纪的MARPOL73／78公约及其附则Ⅱ

国际海事组织目前正在对《ＭＡＲＰＯＬ７３／７８公约》附则Ⅱ－控制散装液体有毒物质污染规则作重大修改，内容包手胡毒液体物质和化学品，这很可能对主管机关、船公司和化工界造成严重的冲击。     

Turnover mechanisms of organic conformation on turbidity in drinking water

The turbidity variation in artificial water and samples from a water plant was investigated in the presence of organics with different relative molecular mass. The results show that recessive turbidity existed when water chemical conditions were changing. The formation of turbidity depended on organic relative molecular mass and their conformations on particles. At higher pH and lower ionic strength, the organic chains with a more extended conformation resulted in rising turbidity of the suspension. At lower pH, the reconformation of organics took place due to charge neutralization by the proton, resulting in a decline in turbidity. The addition of NaCl and MgCl₂ at pH 7.00 also resulted in a decrease of turbidity in the suspension. It is believed that the occurrence of recessive turbidity has a significant influence on the stability of water supply quality.     

聚合硅酸硫酸铝铁的制备与应用

在n(Fe A1)／n(Si)为0．5～1．0、n(Al)／n(Fe)为2．5～3．0、SiO2质量分数为2．3％、硅酸钠溶液的活化pH为5．5、硅酸钠溶液的活化时间为12min或SiO2的质量分数为2．0％、硅酸钠溶液的活化pH为6．0、硅酸钠溶液的活化时间为3min的条件下，制备出的聚合硅酸硫酸铝铁对废水的除浊效果最佳，除浊率大于98％。     

Removal of Alachlor from Water by Catalyzed Ozonation in the Presence of Fe2+, Mn2+, and Humic Substances

Abstract

The effects of Fe(II), Mn(II) and humic substances on the catalyzed ozonation of alachlor, an endocrine disruptor were investigated. Results revealed that small amounts of Fe(II), Mn(II), and humic substances could enhance the ozonation of alachlor, but larger amounts of them would retard the oxidation. These results were successfully identified by an electron paramagnetic resonance (EPR) spectroscopy/spin-trapping method that could quantify hydroxyl radicals. The production of hydroxyl radicals was obviously increased with the increasing of Fe(II) concentration, which contributed to enhance ozonation at low concentrations. But the excess Fe(II) consumed some of the radicals when it was added at a higher concentration (1.5 mg/L). However, no obvious radicals were observed when a different amount of Mn(II) was used, and the catalytic ozonation of alachlor by Mn(II) mainly followed the mechanism of “active sites created on the surface of MnO₂.” The radical pathway was followed when alachlor was ozonated with different concentrations of humic substances because of its radical initiating, promoting, and inhibiting effects.     

汽车零部件金属卤素灯阳光模拟试验与户外自然曝晒的相关性研究

目的 探究汽车零部件金属卤素灯阳光模拟加速试验与户外自然曝晒的关系。方法 使用3种典型高分子透明材料分别进行阳光模拟加速试验、AIMBOX/Arizona户外曝晒和Florida户外曝晒,基于试验后样品的黄变值,比较阳光模拟试验与户外曝晒的相关性,并对阳光模拟试验与户外曝晒的加速性进行探讨。结果 阳光模拟（IP/DP箱）加速试验与AIM BOX/Arizona户外曝晒高度相关,综合加速倍率约是AIM BOX/Arizona户外曝晒的3倍。阳光模拟（IP/DP箱外）加速试验与Florida户外曝晒高度相关,综合加速倍率是Florida户外曝晒的7倍。结论 基于3种典型材料研究可知,汽车零部件阳光模拟加速试验与典型户外自然曝晒具有一定相关性。     

膜生物反应器中膜污染层胞外多糖性质及污染特征

胞外多糖是污水处理膜生物反应器中的重要膜污染物质,经醇析、Sevag法去除蛋白质、层析纯化、透析、冷冻干燥得胞外多糖样品。紫外光谱扫描鉴定该胞外多糖样品不含核酸及蛋白质,分别采用HPLC、GC、FT-IR及SEM等手段对其性质进行分析,考察其对聚偏氟乙烯膜的污染特征。结果表明,所得胞外多糖的重均分子量Mw为4.8×106,糖苷键类型主要为1-3和1-6型,是由葡萄糖、鼠李糖、木糖、甘露糖等组成、具有高度分枝网状结构的杂多糖。胞外多糖膜污染过程受沉积层控制,膜的主要污染形式为胞外多糖在膜表面的沉积。     

Partitioning of water soluble organic carbon in three sediment size fractions： Effect of the humic substances

Water soluble organic carbon (WSOC) in sediments plays an important role in transference and transformation of aquatic pollutants. This article investigated the inherent mechanisms of how sediemnt grain size affect the partitioning coeffcient (k) of WSOC. Influences of NaOH extracted humic substances were particularly focused on. Sediments were sampled from two cross-sections of the middle Yellow River and sieved into three size fractions (< 63 μm, 63-100 μm, and 100--300 μm). The total concentration of WSOC in sediments (CWSOC) and k were estimated using multiple water-sediment ratio experiments. Results show that CWSOC ranges from 0.012 to 0.022 mg/g, while k ranges from 0.8 to 3.9 L/kg. Correlations between the spectrum characteristics of NaOH extracted humic substances and k were analyzed. Strong positive correlations are determined between k and the aromaticity indicators of NaOH extracted humic substances in different sediment size fractions. Comparing with finer fractions (< 63 μm), k is higher in larger size fractions (63--100 and 100--300 μm) related to higher aromaticity degree of NaOH extracted humic substances mostly. While negative relationship between k and the area ratio of fourier transform infrared spectroscopy (FT-IR) at 3400 and 1430 cm-1 implied that the lowest k was related to the highest concentration of the acidic humic groups in particles < 63 μm. WSOC in finer fractions (< 63 μm) is likely to enter into pore water, which may further accelerate the transportation of aquatic contaminants from sediment to water.     

Ⅰ Ⅱ-ASBR中厌氧颗粒污泥的微生物组成及特性

在35℃下以奶粉人工合成废水为底物连续运行了两段厌氧反应器(ⅠⅡ-ASBR),且于ⅠⅡ两柱中形成了两种不同的厌氧颗粒污泥,为了解厌氧颗粒污泥的微生态结构及生物学特性,对ⅠⅡ两柱中厌氧颗粒污泥的形态及微生物组成进行扫描电镜观察,并测定了其不同基质中的比产甲烷活性、辅酶F420和胞外多聚物的含量。结果表明:ⅠⅡ-ASBR反应器ⅠⅡ两柱中厌氧颗粒污泥形态及微生物组成差异明显,Ⅰ柱的厌氧颗粒污泥大而密实,Ⅱ柱的较小,呈多孔的网状结构,Ⅰ柱中厌氧颗粒污泥以甲烷八叠球菌、球菌及短杆菌为主,丝状菌较少,Ⅱ柱则以丝状菌、短杆菌为主,球菌较少;Ⅰ柱颗粒污泥利用葡萄糖、甲酸、丙酸的产甲烷活性较高,利用乙酸的活性相对较低,Ⅱ柱颗粒污泥利用葡萄糖、乙酸的产甲烷活性较高,而利用甲酸、丙酸的产甲烷活性较低;辅酶F420的含量Ⅱ柱比Ⅰ柱明显要高,而胞外多聚物含量Ⅰ柱比Ⅱ柱的高。     

阳离子型聚合物对低温低浊水的絮凝效果与形态学特性

采用微絮凝-深床直接过滤工艺,以西安市曲江水厂低温低浊水质为原水(水温低于10 ℃,初始浊度低于10NTU),投加阳离子型聚合物(简称CP)作主混凝剂或助凝剂,借助分形数学理论与图像分析技术,对滤料粒径、原水浊度、原水温度、药剂种类、聚合物分子量及投加量、混合强度等因素对处理效果的影响进行了研究,分析探讨了不同药剂处理低温低浊水的作用机理、絮凝形态学特征以及絮体结构的分形特性.结果表明,①当温度低于4 ℃、初始浊度小于4NTU时,不宜单独采用Al2(SO4)3或PAC作为絮凝剂;当温度为4～10 ℃、初始浊度小于10NTU时,如果只投加Al2(SO4)3或PAC作为絮凝剂,宜用细砂滤料过滤;低温低浊条件下,无机混凝剂形成的絮体粒径小、结构松散脆弱、有效质量密度低、沉速慢,但表征絮体分形特性的分维值较高.②CP作絮凝剂能显著改善低温低浊水的絮凝效果与过滤性能,但混合强度需增大,宜用粗砂滤料过滤;③单独用CP作絮凝剂时,宜投加分子量较低的弱阳性聚合物或投加低剂量较高分子量的强阳性聚合物;CP用作助凝剂时,能显著减少主混凝剂用量,但宜投加强阳性聚合物或增加弱阳性聚合物的剂量.④CP兼备电性中和与吸附架桥絮凝作用,能形成粒径较大、吸附性能与过滤性能良好的网状絮体构型,其有效质量密度高,产生的污泥量少,污泥沉降速度快,脱水效果好,但分维值低.⑤各种水处理药剂的处理效果为:Al2(SO4)3(或PAC) CP＞CP＞PAC＞Al2(SO4)3,这种差别由絮体的形态学特性与构型特征各异引起.