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)     

供水管网生物膜有机物的二氯乙腈与二氯乙酰胺生成特性

在饮用水输配系统中,来源于管壁生物膜的有机物可能耗氯并生成消毒副产物(DBPs),包括二氯乙腈(DCAN)与二氯乙酰胺(DCAcAm)等高毒性含氮DBPs(N-DBPs).研究考察管网常见的细菌与其胞外聚合物(EPS)以及模拟管壁生物膜氯化与氯胺化后DCAN与DCAcAm的生成,并与天然有机物(NOM)和水源水有机物进行比较.结果显示,铜绿假单胞菌、恶臭假单胞菌与藤黄微球菌与氯反应生成的DCAN、DCAcAm浓度分别为1.48～2.02、0.21～0.38μg·mg~(-1)(mg~(-1)以TOC计),高于同反应条件下NOM的生成量;相比于氯化反应,3株细菌细胞氯胺化生成的DCAN与DCAcAm浓度明显更低.3株菌的EPS也是氯与氯胺化反应生成DCAN与DCAcAm的前体物,且其氯胺化反应生成的DCAcAm浓度高于氯化反应生成的.与NOM、水源水相比,模拟管壁生物膜氯化后生成的N-DBPs与三氯甲烷(TCM)浓度比更高,表明生物膜有机物比NOM与水源水有机物更倾向生成DCAN与DCAcAm类N-DBPs,且模拟管壁生物膜氯胺化的DCAcAm生成量高于氯化反应的,说明管壁生物膜有机物是供水管网系统中DCAN与DCAcAm类N-DBPs的重要前体物.     

焦化废水处理过程中固相物质的形成及处置方法评价

焦化废水处理过程中产生的焦油、污泥和结晶杂盐等固相物质,既有资源属性,又有污染特性,但目前缺乏基于能源、经济及环境影响方面的评估.本研究阐述了3类固相物质的形成机制,建立了质量当量计算及处置方法评价模型.以宝武集团韶关钢铁股份有限公司焦化厂（二期）焦化废水处理工程的A/O/H/O（厌氧/好氧/水解/好氧）流化床工艺作为考察对象,利用工程运行参数和水质统计数据进行固相物质的产量推算,结果发现,焦油、物化污泥、生物污泥（含水率为80%）和工业杂盐的产率分别为0.186、5.80、4.24和1.97 kg·m^-3.通过处置方法评价模型明确了焦油焚烧、污泥热解、结晶杂盐分盐提纯后工业应用是最佳处置方案,在60 m³·h^-1废水处理规模的固相物质处置过程中,每年约产生1177 MWh的能源,获得135.0万元的经济效益,排放627.0 t CO₂,表明能源回收、经济效益和环境影响的协同存在.     

Influence of floc dynamic protection layer on alleviating ultrafiltration membrane fouling induced by humic substances

Cake layer formation is inevitable over time for ultrafiltration (UF) membrane-based drinking water treatment. Although the cake layer is always considered to cause membrane fouling, it can also act as a “dynamic protection layer”, as it further adsorbs pollutants and dramatically reduces their chance of getting to the membrane surface. Here, the UF membrane fouling performance was investigated with pre-deposited loose flocs in the presence of humic acid (HA). The results showed that the floc dynamic protection layer played an important role in removing HA. The higher the solution pH, the more negative the floc charge, resulting in lower HA removal efficiency due to the electrostatic repulsion and large pore size of the floc layer. With decreasing solution pH, a positively charged floc dynamic protection layer was formed, and more HA molecules were adsorbed. The potential reasons were ascribed to the smaller floc size, greater positive charge, and higher roughness of the floc layer. However, similar membrane fouling performance was also observed for the negative and positive floc dynamic protection layers due to their strong looseness characteristics. In addition, the molecular weight (MW) distribution of HA also played an important role in UF membrane fouling behavior. For the small MW HA molecules, the chance of forming a loose cake layer was high with a negatively charged floc dynamic protection layer, while for the large MW HA molecules it was high with a positively charged floc dynamic protection layer. As a result, slight UF membrane fouling was induced.     

黄渤海区域水产品中全氟烷基物质的分布特征

选取黄渤海区域水产品生产、消费水平较高的23个城市,采集鱼类、海洋贝类、甲壳类、头足类及海珍品（海参、鲍鱼）等5类水产品共1225个样本,采用超快速液相色谱-串联质谱法测定了23种全氟烷基物质（PFASs）的含量,并分析了黄渤海区域水产品中PFASs的残留水平及分布特征.结果表明,黄渤海区域水产品中PFASs的残留水平具有明显的组分差异、城市分布及品种分布差异等特征.在23种PFASs组分中,共检出20种PFASs,其中全氟辛烷磺酸（PFOS）和全氟辛酸（PFOA）的检出率最高,分别为79.1%和71.7%,且PFOA的质量浓度占比最高（64.5%）,为首要污染组分;在不同采样点样本中,莱州湾近岸的潍坊、滨州和东营,渤海湾近岸的沧州以及辽东湾近岸的营口为PFASs总质量浓度（∑PFASs）较高的城市,残留水平范围为10.2~16.8μg/kg;在不同品种样本中,检出PFASs组分的数量由高到低为：鱼类（20种） > 海洋贝类、甲壳类（18种） > 海珍品（16种） > 头足类（10种）,其中海洋贝类、海珍品样本中检出率最高的是PFOA,鱼类、甲壳类样本中检出率最高的是PFOS,而头足类则是全氟辛烷磺酰胺（PFOSA）;通过计算不同水产品中PFASs各组分的平均含量发现,PFOA、PFOS、全氟十一烷酸（PFUdA）和PFOSA在不同品种中平均含量相对较高,且表现出较为明显的组分差异性;通过计算危害指数（HR）评价人体暴露于PFASs的健康风险,得到PFASs各组分的危害指数均 < 1,说明黄渤海区域水产品中残留的PFASs对消费者的潜在健康风险较低.     

Ni2+对好氧颗粒污泥系统性能的影响

以城镇污水处理厂A²/O工艺的回流污泥作为接种污泥,在序批式反应器（SBR）中培养好氧颗粒污泥（AGS）,探究Ni²⁺对AGS系统的影响.结果表明：在25℃的条件下,50d左右培养出成熟的AGS,其形态多呈球状或椭球状,外表分布着少量丝状菌,颗粒污泥粒径主要在2~4mm,MLSS达6000mg/L,SVI维持在40~50mL/g.将Ni²⁺作用于培养出的成熟AGS,Ni²⁺在0~2mg/L的浓度范围内会提高AGS的稳定性,使MLSS上升,SVI降低;同时会促进AGS分泌胞外多聚物（EPS）,EPS组成成分中的蛋白质（PN）明显多于多糖（PS）;Ni²⁺对好氧颗粒污泥去除总氮（TN）的抑制程度要大于COD,最终COD去除率可维持在95%以上,TN去除率可维持在70%以上.     

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。     

改进型石灰混凝法去除城市污水二级出水中有机物的研究

将石灰混凝处理后的沉淀泥渣进行回流，对石灰混凝法进行改进，研究改进后的石灰混凝法对城市污水二级出水中有机物的去除效果。结果表明，活性泥渣回流有利于提高石灰混凝法对城市污水二级出水中有机物的去除。回流位置在石灰投加前、复合絮凝剂投加后，最佳回流量为新泥渣产生量的100％～200％，活性泥渣回流的最佳pH为11．0～11．5；活性泥渣中CaCO3、Mg(OH)2、Fe(OH)3等沉淀物以及有机高分子絮体均有助于提高其对有机物的去除效果，其中Mg(OH)2沉淀物起主导作用；含循环泥渣的活性污泥回流，对有机物的去除效果无明显影响。     

分子生物学技术在水处理中的应用研究进展

利用现代分子生物学技术对微生物进行分析和研究,以解决传统微生物分析成本高、速度慢、准确度较低和灵敏度较差等缺点。介绍分子生物学技术在水处理中的应用现状,并对未来发展方向提出建议。目前分子生物学技术在供水工程中主要用于水中细菌、病毒、原生动物、蠕虫等病原微生物的快速检测以及管网微生物种群的分析,在污水处理中主要用于脱氮除磷过程菌群数量和空间分布的剖析、污泥膨胀成因分析以及监测微生物种群多样性来优化处理工艺。分子生物学技术的深入研究将进一步促进水行业的发展。     

外源Ca2+对SBR启动期活性污泥胞外多聚物的动态影响

利用无机物如Ca~(2+),加快活性污泥反应器启动,强化活性污泥絮体性能和结构稳定性,受到越来越多的重视.采用序批式反应器,研究进水中添加Ca~(2+)对反应器启动期活性污泥沉降性能和胞外多聚物的影响.结果表明运行至28 d,与进水中不添加Ca~(2+)的反应器(对照反应器)相比,进水中添加150 mg·L~(-1)外源Ca~(2+)的反应器中活性污泥MLSS和MLVSS值分别高出了89.6%和75.6%,SVI值则降低了47.9%;活性污泥胞外多聚物总量增加了76.4%,多糖增加了28.8%,蛋白质减少了31.6%,添加150 mg·L~(-1)外源Ca~(2+)的反应器中污泥胞外多聚物中多糖/蛋白质值为68.8,对照反应器的活性污泥胞外多聚物多糖/蛋白质值仅为36.6.三维荧光光谱和红外光谱分析表明外源Ca~(2+)导致活性污泥胞外多聚物组分发生了变化.实验结果为进水中添加外源Ca~(2+)改善活性污泥沉降性能提供了基础数据.