Degradation of indomethacin in river water under stress and non-stress laboratory conditions: degradation products, long-term evolution and adsorption to sediment

The pharmaceutical compound indomethacin is not totally removed in wastewater treatment plants,whose effluents flow into aquatic environments;concentrations in the 0.1-100 ng/L range are commonly found in surface waters,and its fate is unknown.Here,biological,photochemical and thermal degradation assays were conducted under stress and non-stress conditions to estimate its degradation rate in river water and establish its degradation products over time.The results revealed that direct sunlight irradiation promoted the complete degradation of indomethacin(2 μg/L) in less than 6 hr,but indomethacin was detected over a period of 4 months when water was kept under the natural day-night cycle and the exposure to sunlight was partially limited,as occurs inside a body of water.The biological degradation in water was negligible,while the hydrolysis at pH 7.8 was slow.Residues were monitored by ultra-pressure liquid chromatography/quadrupole time-of-flight/mass spectrometry after solid-phase extraction,and six degradation products were found;their structures were proposed based on the molecular formulae and fragmentation observed in high-resolution tandem mass spectra.4-Chlorobenzoic and 2-acetamido-5-methoxybenzoic acids were the long-term transformation products,persisting for at least 30 weeks in water kept under non-stress conditions.Furthermore,the degradation in the presence of sediment was also monitored over time,with some differences being noted.The adsorption coefficients of indomethacin and degradation products on river sediment were calculated;long-term degradation products did not have significant adsorption to sediment.     

Variation of phytoplankton community before an induced cyanobacterial （Arthrospira platensis ） bloom

A cyanobacterial (Arthrospira platensis) bloom was induced in situ by nutrient manipulation in an enclosure. The succession of the phytoplankton community and the water chemistry variations before the appearance of bloom, as well as their relationship, were investigated. The cell pigment variations were studied simultaneously. The Pearson’s correlation analysis showed that there was no significant correlation between water chemistry and green algal or cyanobacterial composition, indicating that water chemistry variations were not suitable to be used as indicators for cyanobacterial-bloom early-warning. However, the diversity index of the phytoplankton community decreased sharply before the bloom appeared. Therefore, the dynamics of phytoplankton community was put forward to be an indicator for cyanobacterial-bloom early-warning. In addition, the cell pigment variations represented the changes of community structure, which should be useful for studying the dynamics of phytoplankton community.     

Alteration of dominant cyanobacteria in different bloom periods caused by abiotic factors and species interactions

Freshwater cyanobacterial blooms have drawn public attention because they threaten the safety of water resources and human health worldwide. Heavy cyanobacterial blooms outbreak in Lake Taihu in summer annually and vanish in other months. To find out the factors impacting the cyanobacterial blooms, the present study measured the physicochemical parameters of water and investigated the composition of microbial community using the 16S rRNA gene and internal transcribed spacer amplicon sequencing in the months with or without bloom. The most interesting finding is that two major cyanobacteria, Planktothrix and Microcystis, dramatically alternated during a cyanobacterial bloom in 2016, which is less mentioned in previous studies. When the temperature of the water began increasing in July, Planktothrix appeared first and showed as a superior competitor for M. aeruginosa in NO₃^?-rich conditions. Microcystis became the dominant genus when the water temperature increased further in August. Laboratory experiments confirmed the influence of temperature and the total dissolved nitrogen (TDN) form on the growth of Planktothrix and Microcystis in a co-culture system. Besides, species interactions between cyanobacteria and non-cyanobacterial microorganisms, especially the prokaryotes, also played a key role in the alteration of Planktothrix and Microcystis. The present study exhibited the alteration of two dominant cyanobacteria in the different bloom periods caused by the temperature, TDN forms as well as the species interactions. These results helped the better understanding of cyanobacterial blooms and the factors which contribute to them.     

Eutrophication development and its key regulating factors in a water-supply reservoir in North China

Yanghe Reservoir is an important source of drinking water for Qinhuangdao City,North China;however,in recent decades this water source has been eutrophic with recurrent summer cyanobacterial blooms.The trophic grade of the system in summer was mesotrophiceutrophic in 1990 and became hypertrophic in 2011.The nutrient availability is extremely high during the entire year,and the water temperature should be the primary driver of the summer blooms.In May-October of 2010 and 2011,abrupt variations were observed in the Secchi depth(SD) and chlorophyll a(Chl-a),and both the correlated analysis of Chl-a-SD and trophic status indices(TSI) deviation(TSI Chl-a-TSI SD) showed that algal cell density dominated light attenuation.During the algal bloom outbreak,the microcystin concentration was found to vary between 0.35-2.12 μg/L in 2010 and 0.11-1.86 μg/L in 2011.The maximum microcystin content was more than two times the safety limit required for drinking water.Inflow discharges were most concentrated in the summer,with periods of lower residence time and the largest water level fluctuation over the entire year.When a high availability of nutrients promoted a high Chl-a concentration in the whole system,it appeared that the instability caused by the decrease in residence time could not produce effective changes in the cyanobacterial abundance.The results indicated that nutrient enrichment in the aquatic systems of Yanghe Reservoir is the most serious problem and that the status would not been modified effectively by increasing hydrological fluctuations(e.g.,decreasing the residence time).Therefore,decreasing the nutrient concentrations is the only route to improve the water quality of this reservoir.     

A zero-valent iron and organic matter mixture enhances herbicide and herbicide degradation product removal in subsurface waters

The pesticide atrazine,its degradation products,and 2,6-dichlorobenzamide(BAM) are persistent in groundwater environment.We studied whether their dissipation can be enhanced with a mixture of a complex carbon source and zero-valent iron(ZVI) called EHC.The application rates were 1.0% and 2.0%(by weight) in subsurface sediments slurries(atrazine 30 mg/L),and 2.0% in 1.5 m pilot-scale sediment columns with groundwater flowing through(atrazine 0.08,desethylatrazine DEA 0.03,BAM 0.02 μg/L).In the slurries under aerobic conditions,atrazine of 0.88 ± 0.14 mg/g of EHC was dissipated chemically,as concentrations did not differ significantly between the slurries and their sterilized controls.No degradation occurred in the slurries under anaerobic conditions.In the pilot-scale columns under water-saturated conditions,atrazine,DEA and BAM were not detected in effluents during 33,64 and 64 days from the beginning of the water flow through EHC columns,respectively,but thereafter traces of compounds could be detected.No atrazine or degradation products(BAM,DEA,deisopropylatrazine,desethyldeisopropylatrazine) could be extracted from the column sediments at the end of the experiment.As a result,the sum of dissipated pesticides was about7.6 μg/g of EHC in columns under water-saturated conditions,and 0.88 mg/g of EHC in slurries under aerobic conditions.EHC can be used to enhance the dissipation of studied pesticides in small quantities,preferentially under aerobic conditions.     

Products of methotrexate during chlorination

Methotrexate(MTX)is a cytotoxic drug widely used in the treatment of tumors,autoimmune diseases and severe asthma. jen00883 This drug has been frequently detected in the aquatic environment with concentrations up to μg/L levels. The MTX present in environmental water might be transformed and removed during chlorination disinfection treatment. In this work,the fate of MTX during aqueous chlorination was investigated in laboratory batch experiments,and the transformation products of MTX were identified. Aqueous solutions of MTX(1 mg/L)were chlorinated by sodium hypochlorite solution at room temperature under neutral p H conditions. Chlorinated products were pre-concentrated with solid-phase extraction(SPE)cartridges and determined by liquid chromatography electrospray ionization tandem mass spectrometry(LC–ESI–MS/MS). The reaction of MTX chlorination exhibited pseudo-first-order kinetics and the half-life time of MTX degradation was calculated to be 1.65 min,when the initial chlorine concentration was 2 mg/L. Two chlorinated MTX congeners,4-amino-3-chlorinated-N10-methylpteroylglutamic(monochloro-MTX)and 4-amino-3,5-dichloro-N10-methylpteroylglutamic(dichloro-MTX)were found in the chlorinated solution. Monochloro-MTX was successfully fractionated by high performance liquid chromatography(HPLC)and its structure was further identified using ~1H nuclear magnetic resonance(NMR)analysis. The presence of the two products in real hospital wastewater was then examined and both compounds were detected. Finally,the effects of MTX and monochloro-MTX on the cell cycle progression in vitro were evaluated using zebrafish liver cell line. It was found that both compounds could inhibit the proliferation of zebrafish liver cells through S phase arrest and their effects on the cell cycle profile had no significant difference.     

Off-flavor compounds from decaying cyanobacterial blooms of Lake Taihu

The effect of cyanobacterial bloom decay on water quality and the complete degradation of cyanobacterial blooms in a short period were examined by an enclosure experiment in Gonghu Bay of Lake Taihu,China.Water quality parameters as well as taste and odor compounds during the breakdown of cyanobacterial blooms were measured.Results showed that the decay of cyanobacterial blooms caused anoxic water conditions,decreased pH,and increased nutrient loading to the lake water.The highest concentrations of dimethyl sulfide (DMS),dimethyl trisulfide (DMTS),and β-cyclocitral were observed in the anoxic water,at 62331.8,12413.3,and 1374.9 ng/L,respectively.2-Methylisoborneol was dominant during the live growth phase of cyanobacterial blooms,whereas DMS and DMTS were dominant during the decomposition phase.Dissolved oxygen,pH,and chlorophyll a were negatively correlated with DMS,DMTS,and β-cyclocitral,whereas total phosphorus,total nitrogen,and ammonium (NH4+-N) were positively correlated with DMS,DMTS,β-cyclocitral,and β-ionone.The experimental results suggested that preventing the anaerobic decomposition of cyanobacterial blooms is an important strategy against the recurrence of a malodor crisis in Lake Taihu.     

Biogenic C-doped titania templated by cyanobacteria for visible-light photocatalytic degradation of Rhodamine B

Cyanobacteria, which occurred in eutrophic water harvest solar light to carry out photosynthesis with high efficiency. In this work, cyanobacteria （Microcystis sp.） were used as biotemplate to synthesize titania structure. The synthesized titania sample had similar morphology to that of the original template in spite of the fragile unicellular structures and extremely high water content of cyanobacterial cells. Incorporation of biogenic C, as well as the morphology inherited from biotemplate improved visible- light absorbance of the titania structure. The sample exhibited higher visible-light photocatalytic activity than commercial titania photocatalyst Degussa P25 for Rhodamine B （RhB） degradation. Compared with those C-doped titania photocatalysts prepared by other methods, cyanobacteria templated titania photocatalyst offer some potential for competitive advantages. The reported strategy opened up a new use for the cyanobacteria. It could also be used for titania in applications such as treatment of polluted water, dye-sensitized solar cells, or other regions.     

Changes of DOM and its correlation with internal nutrient release during cyanobacterial growth and decline in Lake Chaohu, China

The seasonal changes in dissolved organic matter (DOM), and its correlation with the release of internal nutrients during the annual cycle of cyanobacteria in the eutrophic Lake Chaohu, China, were investigated from four sampling periods between November 2020 and July 2021. The DOM fluorescence components were identified as protein-like C1, microbial humic-like C2, and terrestrial humic-like C3. The highest total fluorescence intensity (F_T) of DOM in sediments during the incubation stage is due to the decomposition and degradation of cyanobacteria remains. The lowest humification of DOM and the highest proportion of C1 in waters during the initial cyanobacterial growth indicate that fresh algae are the main source. The highest molecular weight of DOM and F_T of the C2 in sediments during cyanobacterial outbreaks indicate the concurrent deposition of undegraded cyanobacterial remains and microbial degradation. The components of DOM are affected mainly by the dissolved total phosphorus in waters, while the temperature drives the annual cycle of cyanobacteria. The decreasing C1 in sediments and increasing nutrients in waters from the cyanobacterial incubation to outbreak indicate that mineralization of algal organic matter contributes importantly to the release of internal nutrients, with the strongest release of phosphorus observed during the early growth of cyanobacteria. The humic-like C2 and C3 components could also affect the dynamics of internal phosphorus through the formation of organic colloids and organic–inorganic ligands. The results show that the degradation of DOM leads to nutrients release and thus supports the continuous growth of cyanobacteria in eutrophic Lake Chaohu.     

Influence of zeta potential on the flocculation of cyanobacteria cells using chitosan modified soil

Using chitosan modified soil to flocculate and sediment algal cells has been considered as a promising strategy to combat cyanobacteria blooms in natural waters. However, the flocculation efficiency often varies with algal cells with different zeta potential (ZP) attributed to different growth phases or water conditions. This article investigated the relationship between ZP of Microcystis aeruginosa and its influence to the flocculation efficiency using chitosan modified soil. Results suggested that the optimal removal efficiency was obtained when the ZP was between -20.7 and -6.7 mV with a removal efficiency of more than 80% in 30 min and large floc size of >350 μm. When the algal cells were more negatively charged than -20.7 mV, the effect of chitosan modified soil was depressed (<60%) due to the insufficient charge density of chitosan to neutralize and destabilize the algal suspension. When the algal cells were less negative than -6.7 mV or even positively charged, a small floc size (<120 μm) was formed, which may be difficult to sink under natural water conditions. Therefore, manipulation of ZP provided a viable tool to improve the flocculation efficiency of chitosan modified soil and an important guidance for practical engineering of cyanobacteria bloom control.     

水华蓝藻细胞提取物对实验鼠毒理效应研究进展

蓝藻暴发引发的水华造成了严重的生态灾难和健康危害,蓝藻水华污染因其已成为全球性的环境问题而受到关注。蓝藻产生的藻毒素具有潜在致癌作用,与多种消化道肿瘤的发病率升高相关,其毒理学效应及其健康危害性更是学术界研究和关注的热点。水华蓝藻细胞提取物较之纯藻毒素的毒理学效应有很大不同,研究水华蓝藻细胞提取物对哺乳动物的毒理学效应能为蓝藻水华的健康风险评估提供一定的理论依据。水华蓝藻细胞提取物对实验鼠产生的毒理学效应,如脏器细胞凋亡和对各脏器抗氧化酶防御系统的损害;水华蓝藻细胞提取物对实验鼠遗传毒性和促癌或致癌作用研究是目前研究的热点和难点问题。     

三峡水库香溪河库湾夏季蓝藻水华成因研究

为探讨香溪河夏季蓝藻水华发生过程及主要影响因素,于2010年7月19日~8月30日在蓝藻水华暴发区域开展持续监测,并对水华过程进行分析.结果表明,水华持续25d,自7月23日暴发,8月16日逐渐消退,藻密度最高达到108.03′106cells/L,优势藻种为鱼腥藻(Anabaena);自身悬浮机制、固氮机制、能够产生藻毒素抑制其他藻类生长,是鱼腥藻成为优势藻种的主要原因;充足的营养物质、显著的水体分层是水华暴发的必要条件,水华期间蓝藻对硝氮利用显著;在具备充足的营养盐的稳定水体中,水温持续升高、混合层与真光层比值的降低是诱发蓝藻水华的关键因子,并且在混合层与真光层比值为0.5时对蓝藻增殖影响最大.     

铜绿微囊藻生长代谢的密度依赖性特征及分子机制

蓝藻水华是淡水湖库普遍面临的水环境问题,目前水华形成机制研究大多关注外界环境因素而忽略了藻类自身及群体的关键调节作用.因此,本文以初始细胞密度为单一变量,考察了不同初始细胞密度条件下蓝藻生长、营养物质利用、叶绿素、藻毒素、胞外分泌物随时间的变化情况.结果发现,初始细胞密度会影响铜绿微囊藻的环境适应性和生长情况,当接种密度≥1×10⁶ cell·mL^-1,铜绿微囊藻适应期消失,初始细胞密度从1×10⁵ cell·mL^-1增加至1×10⁷ cell·mL^-1,最高细胞密度增加了68%,生长速率提高了21%,并且叶绿素变化趋势与生长情况一致.胞外分泌物随初始细胞密度增加而逐渐增加,有利于蓝藻细胞聚集成膜.当初始细胞密度较低（1×10⁵ cell·mL^-1）时,单细胞藻毒素分泌量反而增加,以提高蓝藻的环境适应能力.在高初始密度（1×10⁷ cell·mL^-1）条件下,铜绿微囊藻主要通过上调丙酮酸代谢和碳代谢,促进细胞生长增殖.因此,细胞密度是影响铜绿微囊藻生长代谢的重要因素,在蓝藻水华形成过程中可能发挥重要作用,水华防治应当在细胞密度较低的阶段进行.     

化学氧化剂对水华蓝藻的控制研究

对比了过氧化氢（H₂O₂）、高铁酸钾（K₂FeO₄）和过碳酸钠（Na₂CO₄）3种氧化剂对自然水体中群体蓝藻生长和光合活性的影响.结果发现,3种氧化剂对蓝藻均有快速的抑制效应,且随着氧化剂浓度的增加抑制效果增强.相同氧化剂浓度下,H₂O₂对水华蓝藻的去除能力强于K₂FeO₄和Na₂CO₄,对蓝藻光合系统Ⅱ的最大光量子产量（F_v/F_m）和有效光量子产量（F_v'/F_m'）的抑制效果也更显著.H₂O₂对不同浓度水华蓝藻的控制实验结果表明,初始藻细胞浓度对H₂O₂控藻效果影响较大,细胞密度越大,H₂O₂降解率增加,抑藻效果急剧下降.当初始藻密度为10μg/L和100μg/L,5mg/L H₂O₂的48h降解率分别为64.9%和97.5%,对藻细胞F_v/F_m的抑制率分别为10%和1%.因此,实施H₂O₂控制蓝藻水华的措施应该尽量在蓝藻水华形成早期,即藻密度较低的时候使用.     

微囊藻毒素［Dha7］MCRR的制备及鉴定

以野外收集的水华蓝藻为原料,经过75％甲醇溶液浸提,快速色谱分离和半制备色谱纯化,从滇池水华蓝藻中分离纯化出1种微囊藻毒素变体。电喷雾质谱、紫外分光光度计和HPLC检测结果表明,所得毒素为[Dha7]MCRR,是MCRR的1种去甲基化变体,其纯度大于 95％。该毒素的分子组成为环(Ala-Arg-MeAsp-Arg-Adda-Glu-Dha),分子量为1023,其紫外扫描光谱（200～300nm）在239nm处有特征吸收。[Dha7]MCRR在滇池水华蓝藻中普遍存在,有时会成为MC的主要种类。     

HA1絮凝剂在供水水库水华应急处理中的应用研究

2006-04华南一座供水水库发生卷曲鱼腥藻（Anabaena circinalis）水华,供水口形成藻细胞的堆积,浮游植物、蓝藻、卷曲鱼腥藻（Anabaena circinalis）的细胞密度分别高达7.3×10⁷、7.2×10⁷、4.1×10⁷ cells·L^-1.为保障正常供水,于04-22～04-30用小孔径的网和防水膜对供水口进行区域分隔,改变水流方向,同时在水面喷射以铁盐为核心的HA1絮凝剂控制水华.处理第1 d,浮游植物、蓝藻、卷曲鱼腥藻（Anabaena circinalis）的细胞密度分别降至5.3×10⁶、4.7×10⁶、2×10⁶ cells·L^-1,去除率分别达到93%、94%和95%.处理期间,藻细胞密度平均为1.2×10⁷ cells·L^-1,最高不超过2.0×10⁷ cells·L^-1,不同藻类门的处理效果不同,蓝藻的数量大幅度下降,绿藻、硅藻的种类和数量略有增加,说明HA1絮凝剂在本次应急处理方案中对蓝藻具有较好的去除效果.     

Stable-isotope probing of bacterial community for dissolved inorganic carbon utilization in Microcystis aeruginosa-dominated eutrophic water

Dissolved inorganic carbon (DIC) is an important source of carbon in aquatic ecosystems, especially under conditions of increased frequency of cyanobacterial bloom. However, the importance of bacteria in direct or indirect utilization of DIC has been widely overlooked in eutrophic freshwater. To identify the functional bacteria that can actively utilize DIC in eutrophic freshwater during cyanobacterial bloom, stable-isotope probing (SIP) experiments were conducted on eutrophic river water with or without inoculation with cyanobacteria (Microcystis aeruginosa). Our 16S rRNA sequencing results revealed the significance of Betaproteobacteria, with similar relative abundance as Alphaproteobacteria, in the active assimilation of H¹³CO₃^? into their DNA directly or indirectly, which include autotrophic genera Betaproteobacterial ammonia-oxidizing bacteria. Other bacterial groups containing autotrophic members, e.g. Planctomycetes and Nitrospira, also presented higher abundance among free-living bacteria in water without cyanobacteria. Microcystis aggregates showed a preference for some specific bacterial members that may utilize H¹³CO₃^? metabolized by Microcystis as organic matter, e.g. Bacteroidetes (Cytophagales, Sphingobacteriales), and microcystin-degrading bacteria Betaproteobacteria (Paucibacter/Burkholderiaceae). This study provides some valuable information regarding the functional bacteria that can actively utilize DIC in eutrophic freshwater.     

风场对太湖梅梁湾水华及营养盐空间分布的影响

为了解风场对湖泊表层蓝藻水华及营养盐空间分布的影响,以太湖梅梁湾为例,在蓝藻水华期间开展表层粒子漂流实验,研究风场对水体表层物质的推移规律,并开展全水域水体表、中、底层密集布点采样,测定水体藻类叶绿素a、氮、磷、高锰酸盐指数、溶解性有机碳、溶解氧等水质指标,探讨风场驱动下大型浅水湖泊蓝藻水华及营养盐时空分布特征.结果表明,在平均风速1. 9 m·s~(-1)和2. 3 m·s~(-1)的情况下,表层粒子的平均漂移速度分别为3. 0 cm·s~(-1)和5. 0 cm·s~(-1);风场对表层水体蓝藻水华的空间分布具有决定性影响,能够引起蓝藻水华在空间上较高的异质性;蓝藻水华物质的空间变化对水体颗粒态氮、磷、有机质和溶解氧等水质指标产生较大影响,表、中、底层颗粒态氮和磷、高锰酸盐指数与叶绿素a浓度的空间分布一致,而溶解态氮、磷浓度及溶解性有机碳的分布与叶绿素a浓度分布不尽相同;蓝藻水华物质在风场作用下的再分配对水体溶解氧产生复杂的影响,底层溶解氧平均值低于表层与中层,可能对沉积物营养盐释放产生影响;依据高密度布点调查估算,仅表层20 cm,梅梁湾水域的蓝藻干物质赋存量约396 t,远大于蓝藻打捞工程的清除量.研究表明,鉴于水华期间风场作用下对蓝藻水华漂移的巨大影响,在湖泊水质调查采样方法及数据分析时应充分考虑蓝藻水华漂移的影响因素;防控湖泛灾害的蓝藻打捞作业对湖体蓝藻水华赋存量的清除能力有限,只能对岸边带湖泛的预防产生影响.     

蓝藻胞外聚合物对供水管网水质的影响

针对游离态蓝藻胞外聚合物（EPS）在常规水处理工艺中不易去除、残留蓝藻EPS极易进入供水管网的特性,研究了蓝藻EPS对供水管网水质变化及生物稳定性的影响.针对管道使用时限分析了不同管道内部产生附膜条件下,蓝藻EPS对供水管网中余氯、浑浊度、生物稳定性、有机组分等主要水质指标变化规律的影响.结果表明,蓝藻EPS加快了管网余氯衰减速度,导致管网水质浑浊度在12~24h后即超出生活饮用水卫生标准上限,并使管网水质生物稳定性降低,BDOC在72h内增加37.2~39.5%,AOC增加365~393%,总活菌数升高18~20倍.阐明了蓝藻水华爆发时期净水厂出厂水残留蓝藻EPS在管网余氯存在前提下,仍然能够作为微生物营养基质和代谢能量,而促进管道内细菌生长繁殖,增加微生物代谢活性,刺激微生物胞外有机组分分泌释放,导致管网水质二次污染.     

蓝藻胞外聚合物对供水管网水质的影响

针对游离态蓝藻胞外聚合物（EPS）在常规水处理工艺中不易去除、残留蓝藻EPS极易进入供水管网的特性,研究了蓝藻EPS对供水管网水质变化及生物稳定性的影响.针对管道使用时限分析了不同管道内部产生附膜条件下,蓝藻EPS对供水管网中余氯、浑浊度、生物稳定性、有机组分等主要水质指标变化规律的影响.结果表明,蓝藻EPS加快了管网余氯衰减速度,导致管网水质浑浊度在12~24h后即超出生活饮用水卫生标准上限,并使管网水质生物稳定性降低,BDOC在72h内增加37.2~39.5%,AOC增加365~393%,总活菌数升高18~20倍.阐明了蓝藻水华爆发时期净水厂出厂水残留蓝藻EPS在管网余氯存在前提下,仍然能够作为微生物营养基质和代谢能量,而促进管道内细菌生长繁殖,增加微生物代谢活性,刺激微生物胞外有机组分分泌释放,导致管网水质二次污染.