蓝藻AOM特征与DBPs生成关系的研究进展

蓝藻水华期间,藻细胞因自然生长或受水处理工艺影响(如预氧化和混凝),会向水中释放大量藻源有机物(AOM),能够与氯消毒剂反应生成大量消毒副产物(DBPs),增加了饮用水安全风险.了解AOM的特征及其对DBPs生成的影响对于AOM的控制和饮用水安全保障至关重要.本文综述了蓝藻AOM的主要理化特征(溶解性有机碳、溶解性有机氮、亲疏水性、光学特性、分子量、化学结构)及其对饮用水处理过程中AOM的削减转化规律和DBPs生成的影响,并讨论了AOM前体表征技术在蓝藻水处理过程中追踪AOM变化和预测DBPs的应用前景,最后展望了未来的研究方向.     

藻屑堆积对沉积物-水界面污染物的释放效应

为探索不同密度藻屑堆积对沉积物-水界面污染物的释放效应,设置了对照组(无藻屑添加)、2个藻屑添加组(分别为1倍组(加入0.06 g干藻,约6 g·m~(-2),以干重计)、20倍组(加入1.2 g干藻,约120 g·m~(-2),以干重计)),于(16±1)℃避光培养.结果表明,实验前4 d,20倍组藻屑分解耗氧剧烈并释放出大量溶解性有机质(DOM)及氮、磷营养盐.其中,溶解氧(DO)浓度迅速下降至1.4 mg·L~(-1)以下,上覆水中类色氨酸类物质荧光强度在第4 d最高(0.8 RU)且高于空白组,对荧光强度的贡献比例高达51.7%,为DOM的主要成分,说明藻屑分解释放大量类色氨酸物质.释放的溶解性无机氮(DIN)、溶解性总磷(DTP)以氨氮(NH_4~+-N)、正磷酸盐(PO_4~(3-)-P)为主要形态.随后实验阶段上覆水中SR值、E250/E360值降低,E253/E203值增加,说明藻屑在降解过程中腐殖化程度逐渐增加,取代基种类减少,导致释放的DOM以类腐殖质为主.因此,20倍组类色氨酸类物质逐渐被降解,导致荧光强度逐渐降低,类腐殖质荧光强度增加,对荧光强度的贡献比例高达62.7%.而对照组与1倍组污染物释放培养期间无显著性差异,DOM及氮、磷营养盐释放浓度均低于20倍组.因此,120 g·m~(-2)藻屑密度堆积情况下可造成水体明显缺氧至厌氧,导致大量氮、磷营养盐及溶解性有机物释放至上覆水中,成为水体富营养化的重要营养源.     

蓝藻水华对太湖水柱反硝化作用的影响

反硝化作用是湖泊水体最主要的脱氮过程,对减轻湖泊的氮素污染和富营养化控制具有重要意义.蓝藻水华暴发和衰亡可能会通过改变水体氮素循环途径及微环境来促使反硝化作用直接在水柱中发生,加速氮的去除.为了验证这一假设,取太湖湖水添加不同生物量的蓝藻和连续10 d的NO_3~--N、PO_4~(3-)-P营养盐,进行蓝藻生长与降解对反硝化影响的模拟实验,测定蓝藻水华期水体藻类生物量和各形态氮浓度的动态变化,同时利用~(15)N同位素添加培养结合膜进样质谱仪(MIMS)实时定量测定反硝化速率.结果表明,蓝藻在生长期吸收氮素转变为颗粒氮,在衰亡期藻细胞通过降解矿化释放了大量的NH_4~+-N,继而转化为NO_3~--N,为反硝化作用提供底物,是大幅度促进水体反硝化作用的关键;反硝化速率(以N2计,下同)最高达到(1 614. 52±301. 57)μmol·(m~2·h)~(-1),是同时期最低蓝藻生物量组反硝化速率[(534. 45±242. 18)μmol·(m~2·h)~(-1)]的3倍,实验结束时添加初始蓝藻生物量倍数最高组的TN去除率达最高(40. 02%),是未添加蓝藻组TN去除率(17. 72%)的2. 26倍,说明蓝藻堆积会显著促进反硝化作用的强度,加速水体氮素的去除.蓝藻衰亡时反硝化速率的快慢受NH_4~+浓度的影响显著,表明附着在藻团的微生物的耦合硝化-反硝化作用是氮盐去除的主要途径.本研究结果表明,水华蓝藻生长期快速吸收氮素转变为颗粒氮,蓝藻死亡降解后通过耦合硝化-反硝化作用加速氮素去除,这可能是太湖夏季氮素浓度降低的原因之一.     

凤眼莲对铜绿微囊藻生长及藻毒素与营养盐释放的影响

针对目前我国凤眼莲治理富营养化水体技术的规模化应用现状,考虑到大面积控养的凤眼莲与暴发的水华蓝藻(尤其是产毒铜绿微囊藻)会在湖湾区短期内密集共存的情况,开展了凤眼莲对产毒铜绿微囊藻生长、生理特性、藻毒素生产与释放影响的研究,另外,也考察了短期共存下藻类营养盐释放与凤眼莲对藻毒素积累的情况.半连续共培养实验结果表明,凤眼莲能够有效抑制铜绿微囊藻的生长,促进藻细胞的衰亡.虽然凤眼莲未对铜绿微囊藻光合系统Ⅱ的电子传递产生影响,但减少了其光合系统中的藻蓝蛋白(PC)含量和藻蓝蛋白/别藻蓝蛋白(PC/APC)水平,10%和20%水体交换率处理的PC/APC水平第8 d时分别降至相应空白对照的54.93%±7.07%和55.81%±1.97%.凤眼莲对铜绿微囊藻形成了一定的氧化伤害,最终促进其抗氧化系统中超氧化物歧化酶比活显著下降,丙二醛含量显著提高,10%和20%水体交换率处理的丙二醛含量第8d时分别升至相应空白对照的2.95倍±0.074倍和2.22倍±0.086倍.凤眼莲通过促进蓝藻的衰亡和分解,加速了营养盐的释放.12 d内,可溶性总氮浓度回升到初始水平,而水体可溶性总磷的释放速度比氮营养盐更快.另一方面,凤眼莲并没有促进铜绿微囊藻毒素的生产,也没有使水体藻毒素含量显著提高.相反,和自然衰减不同,短期内显著促进了水体藻毒素的降解,第12 d时10%和20%水体交换率处理的水体藻毒素分别下降至12.07μg·L-1±0.63μg·L-1和11.36μg·L-1±0.04μg·L-1.而凤眼莲整株的藻毒素短期积累量(FW)仅为5.95 ng·g-1±0.76 ng·g-1.增加水体交换率能够在一定程度上减缓凤眼莲对铜绿微囊藻的伤害,减缓营养盐的释放速度,但对水体藻毒素消减的影响不显著.     

藻类打捞对太湖聚藻区湖泛发生的影响

藻类打捞是多年来控制太湖沿岸藻源性湖泛的主要措施,为科学地指导藻类的打捞、防止湖泛的发生,采用能够模拟太湖风浪与沉积物再悬浮的大型装置,模拟湖泛易发的藻类聚集量下不同打捞频率(1次/d～1次/6 d)对湖泛发生时水体主要视觉指标和敏感指标〔ρ(DO)、E_h、ρ(Fe2+)、ρ(TFe)、ρ(∑S2-)等〕的影响. 结果表明:1次/d和1次/2 d的高打捞频率能够有效预防湖泛的发生,当第4天对照组发生湖泛时,1次/d和1次/2 d打捞频率下ρ(DO)为0.60和0.06,E_h为48和37,ρ(Fe2+)是对照组的79.3%和90.7%,ρ(TFe)是对照组的64.8%和72.3%,ρ(∑S2-)是对照组的62.03%和64.56%;1次/3 d频率虽不能控制湖泛的发生,但能有效推迟湖泛发生时间约2~3 d;而1次/4 d～1次/6 d的低打捞频率既不能预防也不能推迟湖泛的发生. 研究显示,在2.5 kg/(m2·d)鲜藻聚集速率下,1次/2 d的打捞频率是在控制湖泛发生前提下的最经济打捞频率.      

洱海藻类水华高风险期沉积物氮磷释放通量时空变化

选择藻类水华高风险期,研究沉积物氮磷释放通量时空变化及影响因素,以揭示沉积物氮磷释放对洱海水质影响.结果表明:①2009、2013和2018年洱海沉积物氮磷释放通量整体呈上升趋势,与2009相比,2013年增幅较大,而2018年与2013年相比增幅较小;溶解性总氮(DTN)释放通量在11. 71～14. 15 mg·(m~2·d)~(-1),其中有机氮(DON)释放通量在6. 39～8. 42mg·(m~2·d)~(-1),占DTN的58%,无机氮(DIN)释放通量在5. 31～5. 73 mg·(m~2·d)~(-1),占DTN的42%;溶解性总磷(DTP)释放通量在0. 11～0. 14 mg·(m~2·d)~(-1),无机磷(DIP)释放通量在0. 07～0. 09 mg·(m~2·d)~(-1),占DTP的66%,有机磷(DOP)释放通量在0. 04～0. 05 mg·(m~2·d)~(-1),占DTP的34%.②洱海沉积物氮磷释放通量空间差异也较大,其中氮释放通量呈南部北部中部趋势,磷释放通量表现为北部中部南部趋势; 2009、2013和2018年相比,由北向南各湖区氮释放通量增幅分别为17%、13%和23%,磷释放通量增幅分别为19%、28%和29%.③2009、2013和2018年相比,洱海沉积物氮磷含量总体稳定,不是影响其释放通量变化主因,水华高风险期水体pH增加和DO下降是影响沉积物氮磷释放通量变化的重要因素,洱海保护应关注水体环境因子变化导致的沉积物氮磷释放增加问题.     

水质安全的动态超声波强化混凝除藻水处理试验研究

超声波辐射能够破坏蓝藻气囊,在水处理工艺中达到强化蓝藻混凝沉淀的效果.然而不适当的超声处理会进一步破坏蓝藻细胞,导致胞内毒素大量释放,加重水质污染负荷.本研究为获得水质安全的超声波强化混凝沉淀蓝藻水处理方法,采用频率40~120 k Hz的超声波辐射蓝藻水,考察处理后蓝藻混凝沉淀去除效果及藻毒素释放情况.结果表明,频率68~120 k Hz、能量密度59.1~186.4 W·L-1的静态超声波作用10~15 s后进行混凝沉淀,藻类去除率达98%以上,且频率越高效果越好;然而各频率静态超声波作用5 s以上均会导致藻细胞内藻毒素释放.采用内衬吸声棉及动态超声方式,频率120 k Hz、能量密度38.5~196.6 W·L-1超声波作用7.5~30 s后,可避免胞内藻毒素释放,且能去除水中溶解性藻毒素18.7%~30.7%,混凝沉淀后藻类去除率97.0%以上,其它有机物也降低.     

绿潮硬毛藻分解对天鹅湖水体氮磷水平的影响

为了解绿潮硬毛藻衰亡分解对上覆水体营养水平的影响,以荣成天鹅湖不同湖区的沉积物和暴发的硬毛藻为试材,通过室内模拟研究了藻类分解过程中水体氮磷水平及理化性质的变化,并评价了不同湖区沉积物中氮磷的释放潜力.结果表明:硬毛藻衰亡分解使上覆水体中ρ(TN)和ρ(NH₄+-N)均明显上升,并且前期(0~16 d)上升较快,ρ(TN)和ρ(NH₄+-N)最高分别可达12.40和7.98 mg/L;水体中ρ(TP)和ρ(SRP)表现为前期变化不大,19 d后大幅增加,含量变幅分别为0.02~1.14和0.01~0.40 mg/L.在试验中后期(约16 d后),不同湖区沉积物处理的水体中ρ(TN)、ρ(NH₄+-N)、ρ(TP)、ρ(SRP)均表现为有沉积物含藻处理>无沉积物含藻处理>有沉积物无藻处理.在藻分解的条件下,不同湖区沉积物的氮磷释放能力存在很大差异,氮释放量的顺序为湖中心>西北部>南部,而磷表现为西北部>湖中心>南部.在硬毛藻绿潮的衰亡阶段,由于初期藻体营养盐的直接释放和后期促进沉积物内源释放的间接影响,水体中ρ(TN)和ρ(TP)均明显增加,进而加重了天鹅湖水体的富营养化水平.      

UV-C辐照对延滞期6种微藻生长抑制效果

藻类季节性暴发生长是许多地区水源管理中的难题,亟待研发安全高效的控藻方法。该文以我国水源6种典型藻株为研究对象,包括蓝藻铜绿微囊藻、浮游颤藻、水华鱼腥藻,绿藻普通小球藻、斜生栅藻,硅藻针杆藻,采用准平行光束仪进行50~100 m J/cm2UV-C辐照,研究对于延滞期、低初始生物量的藻类生长抑制效果,分析藻种敏感性差异。结果表明,50~100 m J/cm2UV-C剂量对于铜绿微囊藻、水华鱼腥藻和针杆藻具有2~4 d生长抑制效果,100 m J/cm2剂量组9 d后Chl a浓度减量37%~60%,对于普通小球藻和斜生栅藻仅有1~2 d生长抑制效果,100 m J/cm2剂量组9 d后Chl a浓度减量16%~33%,对于浮游颤藻无抑制效果且会加速其生长。在生长能力和光合活性两方面,硅藻(针杆藻)和蓝藻(铜绿微囊藻和水华鱼腥藻)的敏感性均显著高于绿藻(斜生栅藻和普通小球藻)和蓝藻浮游颤藻藻株。     

藻类有机物对纳滤膜去除萘普生效果影响研究

研究了2种藻类(鱼腥藻/小环藻)有机物(AOM)对纳滤膜去除萘普生(NPX)的影响效果.结果表明,在藻类AOM存在的情况下HL纳滤膜对NPX的去除率由63%增加至64.7%(小环藻)和72.7%(鱼腥藻);但同时造成了严重的膜污染,比通量由99.7%下降至89.6%(小环藻)和86.3%(鱼腥藻).研究发现,藻类AOM的中等分子量(1.5~5kDa)发挥了重要的作用,它们主要由疏水性有机物构成,紧密地黏附在膜表面形成滤饼层,使膜表面的疏水性增强.滤饼层的疏水性造成膜通量衰减并提高NPX去除率.研究还表明,鱼腥藻AOM在中等分子的疏水性明显比小环藻的强,造成的膜污染更严重以及更高的NPX去除效果.     

Evaluation of phytoextracting cadmium and lead by sunflower, ricinus, alfalfa and mustard in hydroponic culture

Soil contaminated with heavy metals cadmium(Cd)and lead(Pb)is hard to be remediated.Phytoremediation may be a feasible method to remove toxic metals from soil,but there are few suitable plants which can hyperaccumulate metals.In this study,Cd and Pb accumulation by four plants including sunflower(Helianthus annuus L.),mustard(Brassica juncea L.),alfalfa(Medicago sativa L.), ricinus(Ricinus communis L.)in hydroponic cultures was compared.Results showed that these plants could phytocxtract heavy metals, the ability of accumulation differed with species,concentrations and categories of heavy metals.Values of BCF(bioconcentration factor)and TF(translocation factor)indicated that four species had dissimilar abilities of phytoextraction and transportation of heavy metals.Changes on the biomass of plants,pH and Eh at different treatments revealed that these four plants had distinct responses to Cd and Pb in cultures.Measurements should be taken to improve the phytoremediation of sites contaminated with heavy metals,such as pH and Eh regulations,and so forth.     

Oxidation of As(Ⅲ) by potassium permanganate

The oxidation of As(Ⅲ) with potassium permanganate was studied under conditions including pH, initial As(Ⅲ) concentration and dosage of Mn(Ⅶ). The results have shown that potassium permanganate was an effective agent for oxidizing of As(Ⅲ) in a wide pH range. The pH value of tested water was not a significant factor affecting the oxidation of As(Ⅲ) by Mn(Ⅶ). Although theoretical redox analyses suggest that Mn(Ⅶ) should have better performance in oxidization of As(Ⅲ) within lower pH ranges, the experimental results show that the oxidation efficiencies of As(Ⅲ) under basic and acidic conditions were similar, which may be due to the adsorption of As(Ⅲ) on the Mn(OH)2 and MnO2 resulting from the oxidation of As(Ⅲ).     

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.     

Chlorobenzenes in waterweeds from the Xijiang River （Guangdong section） of the Pearl River

The Xijiang River is the major source of water for about 4.5 millions of urban population and 28.7 millions of rural population. The water quality is very important for the health of the rural population. The concentration and distribution of chlorobenzenes (CBs) in both water and waterweeds collected from 4 stations in the Xijiang River (Gangdong section) of the Pearl River in April and November were determined. The result showed that nearly every congener of CBs was detected. The total contents of CBs (∑CBs) in the river water ranged from 111.1 to 360.0 ng/L in April and from 151.9 to 481.7 ng/L in November, respectively. The pollution level of CBs in the water in April was higher than that in November. The contents of ∑ CBs in waterweeds ranged from 13.53×102 μg/g to 38.27×102μg/g dry weight (dw). There was no significant difference between April and November in waterweeds. The distribution of CBs in roots, caulis, and leaves of Vallisneria spiralis L. showed different patterns. The leaves mainly contained low-molecular-weight CBs(DCBs), whereas the roots accumulated more PCBs and HCBs. The average lgBCFlip (bioconcentration factor) of CBs ranged from 0.64 to 3.57 in the waterweeds. The spatial distribution character of CBs in the Xijiang River was: Fengkai County ＜ Yunan County ＜Yun'an County ＜ Gaoyao County according to the ∑CBs, and the pollution deteriorated from the upstream to the downstream of the Xijiang River. Further analysis demonstrated that the discharge of waste containing CBs may be the main source of CBs pollution in the Xijiang River.     

Degradation of 2,4-dichlorophenol with a novel TiO2/Ti-Fe-graphite felt photoelectrocatalytic oxidation process

Degradation of 2,4-dichlorophenol(2,4-DCP)was studied in a novel three-electrode photoelectrocatalytic(PEC)integrative oxidation process,and the factors influencing the degradation rate,such as applied current,flow speed of O_2,pH,adscititious voltage and initial 2,4-DCP concentration were investigated and optimized.H_2O_2 was produced nearby cathode and Fe~(2 )continuously generated from Fe anode in solution when current and O_2 were applied,so,main reactions,H_2O_2-assisted TiO_2 PEC oxidation and E-Fenton reaction,occurred during degradation of 2,4-DCP in this integrative system.The degradation ratio of 2,4-DCP was 93% in this integrative oxidation process,while it was only 31% in E-Fenton process and 46% in H_2O_2-assisted TiO_2 PEC process.So,it revealed that the degradation of 2,4-DCP was improved greatly by photoelectrical cooperation effect.By the investigation of pH,it showed that this integrative process could work well in a wide pH range from pH 3 to pH 9.     

Effect of copper on the degradation of pesticides cypermethrin and cyhalothrin

The influence of coexisting copper (Cu) ion on the degradation of pesticides pyrethroid cypermethrin and cyhalothrin in soil and photodegradation in water system were studied.Serial concentrations of the pesticides with the addition of copper ion were spiked in the soil and incubated for a regular period of time,the analysis of the extracts from the soil was carried out using gas chromatography (GC).The photodegradation of pyrethroids in water system was conducted under UV irradiation.The effect of Cu~(2 ) on the pesticides degradation was measured with half life (t_(0.5)) of degradation.It was found that a negative correlation between the degradation of the pyrethroid pesticides in soil and Cu addition was observed.But Cu~(2 ) could accelerate photodegradation of the pyrethroids in water.The t_(0.5) for cyhalothrin extended from 6.7 to 6.8 d while for cypermethrin extended from 8.1 to 10.9 d with the presence of copper ion in soil.As for photodegradation,t_(0.5) for cyhalothrin reduced from 173.3 to 115.5 rain and for cypermethrin from 115.5 to 99.0 min.The results suggested that copper influenced the degradation of the pesticides in soil by affecting the activity of microorganisms.However, it had catalyst tendency for photodegradation in water system.The difference for the degradation efficiency of pyrethroid isomers in soil was also observed.Copper could obviously accelerate the degradation of some special isomers.     

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.