海水淡化超滤-反渗透工艺沿程溴代消毒副产物变化规律

研究了海水淡化超滤-反渗透(UF-RO)工艺沿程有机物和溴代消毒副产物(Br-DBPs)变化特征.该海水中含有较高浓度的Br-(45.6~50.9 mg·L-1)和较多的芳香类化合物[比紫外吸收值SUVA为3.6~6.0 L·(mg·m)-1];色氨酸类芳香族蛋白质、富里酸类有机物和溶解性微生物代谢产物是海水中主要的荧光特征有机物.UF-RO工艺进水海水经Na Cl O消毒后,DBPs的种类和浓度显著增加,且增加的主要为Br-DBPs,其中三溴甲烷(CHBr3)占总三卤甲烷(THMs)的70.48%~91.50%,二溴乙酸(Br2CHCO2H)占总卤乙酸(HAAs)的81.14%~100%,二溴乙腈(C2HBr2N)占总卤乙腈(HANs)的83.77%~87.45%.UF膜对THMs、HAAs和HANs的去除率分别为36.63%~40.39%、73.83%~95.38%和100%.RO膜可以完全去除HAAs,但是对THMs不能完全去除.进水海水的抗雌激素活性为0.35~0.44 mg·L-1,氯消毒后增加了32%~69%.海水淡化UF-RO系统生成的DBPs和其他生物毒性物质最终被截留到了UF浓水和RO浓水中.     

操作条件及水质对海水氯消毒过程中消毒副产物生成的影响

氯消毒广泛应用于海水利用的预处理过程中,以减少生物膜淤积,而消毒过程会导致各类消毒副产物(DBPs)的生成,可能会对海洋生态环境具有潜在危害。系统研究了操作条件和水质对海水氯化消毒过程中生成三卤甲烷(THMs)、卤乙腈(HANs)和卤乙酸(HAAs)的影响。结果表明,氯投加量对DBPs生成的影响最大,随着投氯量的增加,THMs、HANs和HAAs的生成量显著增加,在反应初期随反应时间的延长而增加,随后HANs和HAAs的生成量开始缓慢降低而THMs基本保持不变。随着温度升高,THMs的生成量稳步增加,而HAAs和HANs在分别达到30,25℃后生成量达到最大值,之后随温度的升高而降低。p H对THMs、HANs和HAAs生成的影响相反,在酸性条件下HANs和HAAs的生成量最多,而在碱性条件下THMs的生成量最多。THMs、HANs和HAAs的生成量随溴离子浓度的改变无明显变化,但是随着氨氮浓度的升高,THMs、HANs和HAAs的生成种类和生成量均有明显降低。     

浙江省H市供水系统消毒副产物及其健康风险评价

以浙江省H市供水系统为调查对象,采用配有电子捕获器的气相色谱(GC-ECD)检测2座水厂及相应供水管网中18种消毒副产物(DBPs)的含量,深入探讨了DBPs导致的饮用水健康风险及前体物指标与各类DBPs的相关性.结果发现H市饮用水中检出三卤甲烷(THMs)、卤乙酸(HAAs)、卤乙腈(HANs)和三氯硝基甲烷(HNMs)等类消毒副产物,THMs含量最高,HAAs次之.CX水厂出水和供水管网中THMs分别为7. 70～32. 73μg·L~(-1)和9. 00～51. 42μg·L~(-1),HAAs分别为3. 05～21. 30μg·L~(-1)和6. 00～26. 79μg·L~(-1). TH水厂出水和供水管网中THMs分别为8. 65～38. 76μg·L~(-1)和12. 09～42. 04μg·L~(-1),HAAs分别为2. 42～14. 79μg·L~(-1)和2. 80～33. 40μg·L~(-1),2家水厂出厂水和供水管网中消毒副产物浓度均符合《生活饮用水卫生标准》(GB 5749-2006).采用溶解性有机碳(DOC)和UV254表征水样有机物,分析有机物与DBPs的相关性,发现管网水中三氯甲烷(TCM)与DOC和UV254呈显著负相关性.基于EPA推荐的健康风险评价模型对经口摄取途径时氯消毒副产物的致癌和非致癌风险进行计算,发现H市出厂水和管网水中消毒副产物引起的致癌风险分别为5. 94×10-6～4. 76×10-5和5. 94×10-6～5. 56×10-5,非致癌风险分别为0. 91×10-2～4. 20×10-2和1. 26×10-2～4. 72×10-2.致癌风险主要来自THMs,一溴二氯甲烷(BDCM)贡献了最高的致癌风险,非致癌风险主要来自TCM.     

铜绿微囊藻胞内物消毒副产物生成：氯化和溴化比较

为了研究蓝藻水华期间释放的有机物给原水水质及给水处理过程带来的影响,选取优势藻种铜绿微囊藻的胞内物质(IOM)作为前驱体,分析了其结构特征.此外,分别研究了IOM在pH 6.5、7.1及8.4条件下与氯及溴反应后性质的变化及消毒副产物的生成,并进行了相关性分析.结果表明,IOM中以相对分子质量较大的组分(>30×103)为主,其溶解性有机碳(DOC)含量占总量的68.8%.三维荧光光谱(EEM)的结果表明IOM的成分主要以芳香蛋白类物质为主,其单位DOC的荧光强度为92.6 AU·L·mg-1.与氯或溴反应后,芳香蛋白类EEM峰值下降了76.6%~93.3%,且其降低值与三卤甲烷(THMs,R2=0.81)和卤乙酸(HAAs,R2=0.77)的生成量正相关.IOM与氯或溴反应生成的THMs和HAAs浓度均随着pH的增加而增加.溴相比氯与IOM反应可以生成更多的THMs和HAAs,且HAAs的卤代程度更高,但是氯及溴与IOM反应能力的差异随着pH的升高而逐渐减小,即k OBr·IOM/k OCl·IOM相似文献   

氯消毒过程中水中色氨酸产生THMs和HAAs的特征研究

以氨基酸为代表的溶解性含氮有机物在水源水中广泛存在,成为制水工艺消毒副产物的主要前体物之一.选取色氨酸（Trp）为含氮前体物模型,考察了其在消毒工艺中产生受控消毒副产物的途径及影响因素.结果表明,Trp氯化过程经取代,脱羧,水解等一系列反应,可生成卤乙酸（HAAs）,三卤甲烷（THMs）等消毒副产物.THMs和HAAs的生成量随加氯量增加;随接触时间的延长逐渐增加.温度的升高,HAAs的生成量先增大后减少;碱性条件有利于THMs和HAAs的生成.氯胺消毒和遮光条件下可明显减少THMs和HAAs的产生.     

钴活化过一硫酸盐氧化过程中卤代副产物的生成

活化过硫酸盐产生的硫酸根自由基(SO~(·-)_4)可以降解大多数有机污染物,被广泛用于地下水、土壤修复等领域.本研究发现在钴活化过一硫酸盐(PMS)高级氧化过程中,溴离子会被SO~(·-)_4氧化生成自由溴,继而和苯酚反应生成溴代苯酚,最终生成三溴甲烷和二溴乙酸等副产物.当反应液中苯酚初始浓度为0.05 mmol·L~(-1)、Br~-浓度0.2 mmol·L~(-1)、Co~(2+)浓度5μmol·L~(-1)、PMS浓度1 mmol·L~(-1)、p H为6.0时,三溴甲烷和二溴乙酸的生成随反应的进行先增加后降低,在8 h达到最大,分别为10.3μmol·L~(-1)和14.6μmol·L~(-1).卤代副产物的生成随p H的升高而降低.当卤离子总量保持不变,随着溶液中Cl~-/Br~-比例的增加,卤代副产物的生成总量逐渐降低,而含氯副产物的产量逐渐增加.本研究为全面评价过硫酸盐高级氧化工艺在污染控制方面的应用可行性提供了依据.     

供水管网终端消毒副产物分布特征及预测模型

消毒副产物(disinfection by-products, DBPs)是影响饮用水水质的重要指标.以浙江省H市某区域供水点为调查目标,考察终端龙头水及加热器处理后饮用水中DBPs的含量特征,结合水质理化指标,初步确定管网终端DBPs预测模型,评估经口摄入的健康风险.结果表明,H市某供水点龙头水中共检出THMs、HANs和HAAs这3类共计10种DBPs.龙头水中目标DBPs检出率均为100%,THMs、HANs和HAAs质量浓度分别为10.12～28.39、 0.98～5.19和2.65～7.83μg·L~(-1);热水中TBM、TCAN和DBAN的检出率分别为46.43%、 82.14%和92.86%,BCAN未检出,其它DBPs检出率为100%,THMs、HANs和HAAs质量浓度分别为0.60～12.58、 0.02～0.52和2.42～5.86μg·L~(-1).加热处理后THMs和HANs的含量有所降低,总量分别降低84.22%和91.45%,HAAs变化不明显.水质理化指标pH值和SUVA与DBPs呈正相关关系,余氯和氨氮与DBPs呈负相关关系.根据常规指标与DBPs相关性建立THMs多元线性预测模型,相对误差小于10.00%,准确度较高,可用于管网供水终端THMs的预测.基于美国环保署推荐的健康风险评价模型对经口摄取途径时氯消毒副产物的致癌和非致癌风险进行计算,发现H市龙头水和热水中DBPs通过饮水途径的致癌风险分别为(17.24～84.63)×10~(-6)和(25.49～258.82)×10~(-7);非致癌风险分别为(4.17～50.32)×10~(-2)和(6.52～107.74)×10~(-3).龙头水中BDCM对致癌风险的贡献率最大,而热水系统中TCM贡献率最大;龙头水及热水中非致癌风险主要来自于TCM.热水中THMs的削减量最高达到94.38%,致癌风险降低79.00%.     

长三角部分水源水氯化消毒后卤乙酸形成的多元回归模型研究

以长三角比较有代表性的3处水源(太湖、钱塘江、金兰水库)为实验对象,研究不同消毒条件下9种卤乙酸(haloacetic acids,HAAs)的形成及其影响因素,并通过建立多元回归模型来评估水源水氯化后HAAs的形成.结果表明:HAAs的形成水平依次为太湖钱塘江金兰水库,且均以二卤乙酸(dihaloacetic acid,DHAA)、三卤乙酸(trihaloacetic acid,THAA)为主.二氯乙酸(dichloroacetic acid,DCAA)、总二卤乙酸(ΣDHAA)、HAA5(USEPA规定的5种HAAs)、HAA9(9种HAA的简称)的回归模型具有良好的预测潜力,准确率达83.3%~94.4%,而三氯乙酸(trichloroacetic acid,TCAA)、一溴二氯乙酸(bromodichloroacetic acid,BDCAA)、ΣTHAA(总三卤乙酸)模型的预测准确率较低,只有47.2%~61.1%.根据偏相关系数分析,影响DCAA、ΣDHAA、HAA5的关键的因子是溶解性有机碳;影响TCAA、ΣTHAA、HAA9的关键的因子是投氯量;影响BDCAA形成的最关键因子是溴离子.     

配水管网中生物稳定性和消毒副产物的变化及相关性

研究了上海市2条不同水源水厂配水管网中可同化有机碳（AOC）、三卤甲烷（THMs）和卤乙酸（HAAs）的变化情况,并对饮用水生物稳定性和消毒副产物间的相关性进行了分析.结果表明,管网中AOC和HAAs含量受余氯和微生物活动双重作用的影响,在距水厂较近、余氯较高的管网中,可能因氯与有机物继续反应出现上升,在余氯较低的管网末梢则因为微生物降解作用使含量下降;THMs含量则只受余氯的影响,随管网延伸持续增长.HAAs与AOC含量间存在较好的线形关系,前体物间具有相似性,THMs与AOC含量间呈正相关性;作为饮用水安全性的2个重要方面,生物稳定性和消毒副产物间具有内在的关联性.     

长距离供水系统中消毒副产物分布特征及二次加氯的影响

供水管网覆盖区域大,导致出厂消毒剂量不足以维持管网末梢余氯量,需进行途中二次投氯.以H市供水管网为目标,通过均匀布点采样分析,考察二次加氯消毒型管网中消毒副产物(disinfection by-products,DBPs)的分布特征.结果表明,管网中检出DBPs包括三氯甲烷(TCM)、一溴二氯甲烷(BDCM)、二溴一氯甲烷(DBCM)、三溴甲烷(TBM)、二氯乙酸(DCAA)、三氯乙酸(TCAA)、二氯乙腈(DCAN)、溴氯乙腈(BCAN)和三氯硝基甲烷(TCNM)等,所检水样中DBPs浓度均低于《生活饮用水卫生标准》(GB 5749-2006)规定的标准限值.二次加氯前检出质量浓度(以平均值±偏差表示)分别为:(8.08±3.34)、(9.77±2.91)、(7.38±4.82)、(2.65±2.02)、(2.95±3.26)、(6.02±6.06)、(3.13±2.48)、(1.61±2.05)和(0.15±0.10)μg·L~(-1).二次加氯后检出质量浓度分别为:(10.30±4.55)、(11.73±3.60)、(8.23±5.22)、(2.95±2.45)、(3.29±3.60)、(8.15±7.58)、(3.31±2.61)、(1.33±2.04)和(0.12±0.06)μg·L~(-1).二次加氯后DBPs含量相较于出厂水至二次加氯点呈明显上升趋势,三卤甲烷(THMs)和卤乙酸(HAAs)分别比前段管网含量升高6.32%～26.60%和5.32%～42.71%.此外,原水水质和季节变化对DBPs的形成有一定影响,夏季DBPs的水平普遍高于春季或秋季.出厂水及管网水DBPs生成势分析表明,H市供水系统中DBPs可能存在超标风险,后续需考虑进一步优化处理工艺以保障供水水质.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.     

Removal of cadmium using MnO2 loaded D301 resin

MnO2 loaded weak basic anion exchange resin D301 （Anion exchange resin, macroreticular weak basic styrene） as adsorbent has been prepared and applied to the removal of cadmium. The adsorption characteristics have been investigated with respect to effect of pH, equilibrium isotherms, removal kinetic data, and interference of the coexisting ions. The results indicated that the Cd^2＋ could be efficiently removed using MnO2 loaded D301 resin in the pH range of 3-8 from aqueous solutions with the co-existence of high concentration of alkali and alkaline-earth metals ions. The saturate adsorption capacity of the Cd^2＋ was 77.88 mg/g. The adsorption process followed the pseudo first-order kinetics. The equilibrium data obtained in this study accorded excellently with the Langmuir adsorption isotherm.     

Effect of coagulation pretreatment on the fouling of ultrafiltration membrane

The purpose of this study is to understand the effect and mechanism of preventing membrane fouling, by coagulation pretreatment, in terms of fractional component and molecular weight of natural organic matter （NOM）. A relatively higher molecular weight （MW） of hydrophobic compounds was responsible for a rapid decline in the ultrafiltration flux. Coagulation could effectively remove the hydrophobic organics, resulting in the increase of flux. It was found that a lower MW of neutral hydrophilic compounds, which could remove inadequately by coagulation, was responsible for the slow declining flux. The fluxes in the filtration of coagulated water and supernatant water were compared and the results showed that a lower MW of neutral hydrophilic compounds remained in the supernatant water after coagulation could be rejected by a membrane, resulting in fouling. It was also found that the coagulated flocs could absorb neutral hydrophilic compounds effectively. Therefore, with the coagulated flocs formed on the membrane surface, the flux decline could be improved.     

Penetration analysis of elements and bioleaching treatment of spent refractory for recycling

Acidithiobacillus ferrooxidans ATCC23270 and Acidithiobacillus thiooxidans TM-32 were used for bioleaching of spent refractories of aluminium and copper melting furnaces for their recycling.Firstly,penetration of elements into aluminium melting furnace refractory was investigated and it was found that up to 7 cm from surface was contaminated.Comparison on leaching efficiency by the strains ATCC23270 and TM-32 found that the strain ATCC23270 could treat larger amount of the refractories than the strain TM-32 could do.In the experiment of bioleaching of spent refractory aluminium melting furnace by the strain ATCC23270,high leaching efficiency were obtained on Al,Si,and Ca,and extremely low leaching performance was,however,shown on the rest of elements i.e.,Na,Mn,and Zn.Under the strain TM-32 use,relatively high leaching performance was recognized on Al,Si,Ca,Na,Mn,and Zn.In the experiment of bioleaching for spent refractory copper melting furnace,almost the same leaching trends were shown on Cu,Zn,Al,and Si under the strains ACTT23270 and TM-32 uses.     

Simultaneous removal of ammonium and phosphate by zeolite synthesized from coal fly ash as influenced by acid treatment

Zeolite synthesized from fly ash （ZFA） without modification is not efficient for the purification of NH4＋ and phosphate at low concentrations that occur in real effluents, despite the high potential removal capacity. To develop an effective technique to enhance the removal efficiency of ammonium and phosphate at low concentrations, ZFA was modified with acid treatment and the simultaneous removal of ammonium and phosphate in a wide range of concentration was investigated. It was seen that when compared with untreated ZFA, only the treatment by 0.01 mol/L of H2SO4 significantly improved the removal efficiency of ammonium at low initial concentrations. The behavior was well explained by the pH effect. Treatment by more concentrated H2SO4 led to the deterioration of the ZFA structure and a decrease in the cation exchange capacity. Treatment by 0.01 mol/L H2SO4 improved the removal efficiency of phosphate by ZFA at all initial P concentrations, while the treatment by concentrated H2SO4 （≥0.9 mol/L） resulted in a limited maximum phosphate immobilization capacity （PIC）. It was concluded that through a previous mild acid treatment （e.g. 0.01 mol/L of H2SO4）, ZFA can be used in the simultaneous removal of NH4＋ and P at low concentrations simulating real effluent.