两种咪唑氯盐类离子液体对水稻幼苗根部的毒性效应

按照毒性试验标准方法研究了1-癸基-3-甲基咪唑氯盐([DMIM]Cl)、1-十二烷基-3-甲基咪唑氯盐([C12MIM]Cl)对水稻幼苗生长的影响,测定了水稻根的半数抑制浓度(IC50-5d)、超氧化物歧化酶(SOD)活性、过氧化氢酶(CAT)活性、过氧化物酶(POD)活性、水稻根部丙二醛(MDA)含量及对水稻根系的生理影响.结果表明:两种离子液体(ILs)对水稻幼苗根部生长均具有抑制作用,随着浓度的增大抑制率增加,[DMIM]Cl和[C12MIM]Cl的根长IC50-5d分别为0.10 mg·L-1和0.054 mg·L-1,水稻幼苗根部对两种ILs均有氧化应激反应,在[DMIM]Cl和[C12MIM]Cl处理下,3种抗氧化酶活性均受到严重抑制,丙二醛(MDA)含量升高,加剧了水稻幼苗根部细胞膜脂质过氧化作用.[DMIM]Cl和[C12MIM]Cl处理导致根系活力降低,根系质膜透性增大.     

Influencing factors of disinfection byproducts formation during chloramination of Cyclops metabolite solutions

Effects of reaction time, chlorine dosage, pH and temperature on the formation of disinfection byproducts(DBPs), were investigated during the chloramination of Cyclops metabolite solutions. The results showed that some species of DBPs like trichloromethane(TCM), dichloroacetic acid(DCAA) and trichloroacetic acid(TCAA) could accumulate to their respective stable values with a progressive elevation in reaction time and monochloramine concentration. And 1,1,1-2-trichloropropanone(1,1,1-TCP) content decreased correspondingly with a continuous increase of reaction time. The amounts of chloral hydrate(CH), chloropicrin(TCNM), 1,1,1-TCP and DCAA firstly increased and then decreased with increasing monochloramine doses. Higher temperature resulted in a decrease of CH, dichloroacetonitrile(DCAN), 1,1-dichloropropanone(1,1-DCP), 1,1,1-TCP, DCAA and TCAA concentration. pH affected the formation of the different DBPs distinctly. TCM accumulateded with the increase of pH under 9, and DCAA, TCAA, CH and 1,1-DCP decreased continuously with increasing pH from 5 to 10, and other DBPs had the maximum concentrations at pH 6–7.     

Effect of activated sludge treatment on the formation of Nnitrosamines under different chloramination conditions

Municipal wastewater discharge is considered as one of the main sources of N-nitrosamine precursors which can impact the qualities of downstream source waters and reclaimed wastewaters for potable reuse. NNitrosamine precursors can be removed to various degrees during biological wastewater treatment (e.g., the activated sludge (AS) process). So far, little is known about the impact of the AS process on N-nitrosamine formation under practical disinfection condition (e.g., uniform formation condition (UFC)). In this study, N-nitrosamine UFC from selected model compounds, sewage components (i.e., blackwaters and greywaters) and sewage samples were comprehensively investigated during batch AS treatment tests. NNitrosodimethylamine (NDMA) formation from the tested precursor compounds (i.e., trimethylamine (TMA) and sumatriptan (SMTR)) under UFC chloramination decreased mostly after 6 or 24 hr treatment with different types of AS (i.e., domestic rural AS, domestic urban AS, and textile AS), and the reductions in NDMA UFC were comparable to their NDMA formation potential (FP) reductions. In urine and feces blackwaters, NDMA UFC increased after 6 or 24 hr treatment with the domestic (i.e., rural and urban) AS, while NDMA FP decreased substantially. The increases in NDMA UFC after AS treatment was presumably attributed to the removal of bulk organic matters (e.g., dissolved organic carbon (DOC)) which favored NDMA formation under UFC. On the other hand, in laundry greywaters having relatively abundant DOC, N-nitrosamine UFC was less affected by DOC removal before or after AS treatment, but decreased to similar degrees with N-nitrosamine FP. In sewage samples collected from wastewater treatment plants, N-nitrosamines UFC tended to increase or remain constant during AS treatment, despite the decreases in their FPs. These results suggest that biological wastewater treatment (e.g., the AS process) may not effectively reduce N-nitrosamine formation (e.g., measured under UFC) partially because the concurrent removal of bulk organic matters (e.g., DOC) favored N-nitrosamine formation in s econdary effluents.     

亚硝氮在氯及氯胺消毒中形成三氯硝基甲烷的作用研究 ——以色氨酸为例

以溶解有机碳为5 mg·L-1的色氨酸溶液为研究对象,探索氯和氯胺消毒时,不同影响因子对亚硝氮在三氯硝基甲烷(TCNM)形成中的作用,从而识别其关键消毒因子.结果表明:NO-2的加入对TCNM的形成有明显的促进作用.对氯消毒来说,NO-2对TCNM形成的促进作用在酸性条件下(TCNM增量为11.82μg·L-1)比碱性条件下(TCNM增量为2.66μg·L-1)更为明显;而对于氯胺,却在中碱性条件下较为明显(pH=5,6,7,8,9,TCNM的增量分别为0.04、0.11、0.50、0.34、0.27μg·L-1).但不管是氯消毒还是氯胺消毒,NO-2对TCNM形成的促进作用基本随着消毒剂量、反应时间的增加而增加.由极差分析得知,氯、氯胺消毒下影响NO-2对TCNM形成的关键的因子均是pH值.     

Impact of chlorine exposure time on disinfection byproduct formation in the presence of iopamidol and natural organic matter during chloramination

Chloramines,in practice,are formed onsite by adding ammonia to chlorinated drinking water to achieve the required disinfection.While regulated disinfection byproducts(DBPs)are reduced during chloramine disinfection,other DBPs such as iodinated(iodo-)DBPs,that elicit greater toxicity are formed.The objective of this study was to investigate the impact of prechlorination time on the formation of both halogen-specific total organic halogen(TOX)and iodo/chlorinated(chloro-)DBPs during prechlorination/chloramination in source waters(SWs)containing iopamidol,an X-ray contrast medium.Barberton SW(BSW)and Cleveland SW(CSW)containing iopamidol were prechlorinated for 5–60 min and afterwards chloraminated for 72 hr with ammonium chloride.Chlorine contact time(CCT)did not significantly impact total organic iodine(TOI)concentrations after prechlorination or chloramination.Concentrations of total organic chlorine(TOCl)formed during prechlorination did not significantly change regardless of pH and prechlorination time,whileTOClappearedtodecreaseafter 72 hrchloraminationperiod.Dichloroiodomethane(CHCl_2I)formation during prechlorination did not exhibit any significant trends as a function of p H or CCT,but after chloramination,significant increases were observed at pHs 6.5 and 7.5 with respect to CCT.Iodo-HAAs were not formed during prechlorination but were detected after chloramination.Significant quantities of chloroform(CHCl_3)and trichloroacetic acid(TCAA)were formed during prechlorination but formation ceased upon ammonia addition.Therefore,prechlorination studies should measure TOX and DBP concentrations prior to ammonia addition to obtain data regarding the initial conditions.     

咪唑类离子液体系列对卤虫的急性毒性研究

选取卤虫作为实验生物,研究了1-丁基,1-辛基,1-十二烷基-3甲基咪唑盐酸盐( [Cnmim][Cl](n = 4,8,12) ) 3种离子液体的暴露对卤虫个体存活率的影响.同时,选取了实验室常用的有机试剂甲醇和乙腈,无机化学品重铬酸钾作为阳性对照.根据剂量效应曲线的拟合结果发现,受试离子液体系列随着咪唑环上烃基侧链碳原子数的增加,对卤虫的毒性效应也相应增强,3种离子液体对卤虫的LC50-24h依次为171.1,133.6,17.76μg/mL.离子液体对卤虫的LC50-24h比甲醇(LC50-24h=84.83mg/mL)和乙腈(LC50-24h=52.84mg/mL)低了2~3个数量级,重铬酸钾对卤虫的(LC50-24h=16.87μg/mL)与离子液体对卤虫的LC50-24h处于同一水平.     

氯、氯胺消毒下钱江源水源水消毒副产物形成特征研究

以钱江源水源水为研究对象,以氯、氯胺为消毒方式,研究了不同消毒条件下,三卤甲烷(THMs)、卤乙腈(HANs)、氯代酮(CKs)、二卤乙酸(DHAAs)、三卤乙酸(THAAs)等消毒副产物(DBPs)的形成情况,以便为水务工作者监测钱江源建库前后水质、DBPs形成的变化提供基础数据.结果显示,氯消毒下DBPs的产量比氯胺消毒高出3~7倍甚至1个数量级,但不管是氯消毒还是氯胺消毒,THMs、HAAs形成量均在我国饮用水标准范围内.氯消毒下,大部分DBPs产量为中、碱性条件酸性条件(除了CKs),氯胺消毒则呈现不同的情况(所有DBPs的产量均为p H=6、p H=7p H=8).消毒剂量对所有DBPs形成具有明显的促进作用;溴离子对THMs、DHANs、DHAAs的形成有明显的促进作用.进一步研究表明,钱江源水源水的水质比钱塘江下游九溪水源水好,DBPs形成也较低,某些指标(如有机碳、有机氮、HANs形成量等)甚至比同省水质较好的金兰水库还要好;而且由于其较高的比紫外吸收值(SUVA),DBPs的溴嵌入能力均比九溪水源水、金兰水库低.此外,就目前的钱江源水源水来说,控制消毒剂量(氯、或氯胺)是控制DBPs形成的有效策略.     

离子液体与废水对青海弧菌Q67的混合毒性研究

以1-苄基—3-甲基咪唑四氟硼酸(IL1)和1-已基—3-甲基咪唑双(三氟甲基磺基)亚胺(IL2)及废水为混合物组分,以Vibrio qinghaiensis sp.-Q67为指示生物,采用均匀设计射线法设计不同浓度配比的IL1-IL2混合物体系及IL1-IL2-废水的混合物体系,应用微板毒性分析法系统测定这些混合物体系的浓度-效应数据,并以浓度加和与独立作用模型为加和参考模型分析毒性相互作用.结果表明:IL1-IL2的混合物体系具有拮抗或加和作用,且混合物毒性(pEC50值)与其中IL1的浓度比具有良好的线性关系;IL1-IL2-废水的混合物体系具有明显的协同或加和作用,且混合物pEC50值与其中废水的浓度比具有良好的线性关系.     

聚离子液体修饰荷电超滤复合膜的构建及其抗污染性分析

以氯化-1-烯丙基-3-乙烯基咪唑离子液体为反应单体,偶氮二异丁腈(AIBN)为引发剂,通过自由基聚合先合成聚离子液体预聚物,并将其与聚偏氟乙烯(PVDF)、聚乙二醇(PEG)进一步共混反应,以制备聚离子液体/PVDF共混铸膜液.然后将该铸膜液在聚丙烯(PP)微孔膜表面进行涂覆成膜,以制备具有互穿网络结构的聚离子液体/PVDF荷电复合膜.采用红外光谱、扫描电镜、Zeta电位计等对复合膜表面的化学结构、形貌及荷电性能等进行分析,并采用水通量测定仪对复合膜的纯水通量及蛋白质和染料的分离性能等进行了研究.结果表明,该复合膜表面具有较好的荷电性能,且随聚离子液体的加入可以有效提高膜的亲水性和抗污染性,复合膜M2的纯水通量可达到101.7 L·m-2·h-1,该膜对溶菌酶和染料罗丹明6G的截留率分别为88.0%和94.1%,该分离膜经清水反冲洗后通量恢复率分别达到72.5%和91.8%.     

A preliminary investigation on the use of organic ionic liquids as green solvents for acylation and oxidation reactions

Different organic ionic liquids (OILs) have been used as green solvents in Friedel–Crafts acylation and alcohol oxidation reactions. Specifically, three OILs were employed, 1-ethyl-3-methylimidazolium chloride, tetraethylammonium bromide, and 1-butyl-3-methylimidazolium chloride, and four reactions studied, acylation of toluene by acetyl chloride, acylation of benzene by propionyl chloride, oxidation of benzyl alcohol by N-methylmorpholine N-oxide, and oxidation of salicylic alcohol by o-iodoxybenzoic acid. The reactions were carried out, at room temperature, in a well-stirred lab-scale glass batch reactor, under inert atmosphere and for reaction times ranging from 5 to 90 min. Gas chromatography was employed to characterize the reaction products. First of all, the desired products yield as a function of the reaction time was investigated. Moreover, simple kinetic models were built for the interpretation of the experimental results. Additional tests were carried out to assess the possibility of recycling the OILs employed. The results of this preliminary study were satisfactory as the OILs investigated proved to be good media in which to carry out the reactions studied in this work (desired products yield greater than 90% were achieved). Moreover, the reaction rate expressions of the kinetic models were able to satisfactorily predict the experimental results. Finally, the possibility of recycling the OIL (in one of the reactions) was proved to be feasible and this suggests the use of recycled OIL together with a fresh make-up, to match high yield values with economical/ecological advantages.     

溴化咪唑类离子液体对胞嘧啶结构和性质影响的计算研究

离子液体被称为绿色溶剂得到广泛的应用,但离子液体并非完全无毒性,其中关于离子液体基因毒性的相关实验报道不少.本文运用密度泛函理论M06-2X和ωB97XD方法在6-311++G(2d,p)基组水平,对阳离子(C_(2/4)mim~+)、阴离子(Br~-)、离子液体([C_(2/4)mim]Br)与胞嘧啶(C)作用体系的几何结构、能量学特征、谱学性质和电子结构等进行计算研究.两种方法计算得到5种最稳定结构C-C_2mim-1、C-C_4mim-1、C-Br-1、C_21和C_41,经BSSE校正后的结合能分别为-99.1(-103.9)、-99.6(-104.3)、-102.2(-99.3)、-97.3(-100.7)和-104.5(-105.6)kJ·mol~(-1),体系中胞嘧啶变形能在2.8~6.9 kJ·mol~(-1)范围内.复合物中胞嘧啶的C2=O7和N1―H键的伸缩振动频率均发生一定程度的红移.分子中的原子理论(Atoms in molecule)得到阳离子、阴离子、离子液体与胞嘧啶作用以静电作用为主.自然键轨道分析(Natural bond orbitals)表明C_21和C_41的稳定化能主要来源于LP Br→BD~* N1—H、LP Br→BD~* N1―C2和LP O7→BD~* C2―H之间的相互作用.极化连续介质模型(Polarizable continum model)计算表明水溶液环境可削弱溴化咪唑类离子液体对胞嘧啶结构和性质的影响.     

两种常用兽药对作物发芽的生态毒性效应

采用室内生长箱培养的试验方法,研究了2种常用兽药磺胺嘧啶钠、环丙沙星对小麦、白菜和番茄种子发芽、根伸长、芽伸长的影响,分析了兽药和作物生长之间的剂量.效应关系,比较分析了小麦,白菜和番茄对2种兽药胁迫的敏感性.结果表明,根长抑制率和芽长抑制率与兽药浓度显著相关(p<0.05);种子发芽抑制率与2种兽药浓度不相关(p>0.05).2种兽药对根伸长和芽伸长的抑制明显强于对种子发芽的抑制.3种作物对磺胺嘧啶钠胁迫的敏感性依次为小麦＞白菜＞番茄;对环丙沙星胁迫的敏感性依次为白菜＞番茄＞小麦;磺胺嘧啶钠对3种作物的毒性效应明显强于环丙沙星.     

水环境中溴化1-烷基-3-甲基咪唑类离子液体与胸腺嘧啶相互作用体系的计算研究

溴化咪唑类离子液体的生物小分子作用机制亟待探索.本文采用M06-2X/6-311++G（2d,p）/PCM/water理论方法计算了研究胸腺嘧啶（T）与溴化1-烷基-3-甲基咪唑类离子液体（[C_nmim]Br,n=2、4、6、8、10）相互作用形成的T-[C_nmim]⁺、T-Br^-、T-[C_nmim]Br和T-2[C_nmim]Br体系的结构和能量学特征.结果表明T与阴阳离子间形成典型构型的稳定顺序是：共面 < 垂直 < 堆积（T-[C_nmim]⁺）,top < front（T-Br^-）,T-[C_nmim]⁺ < T-Br^- < T-[C_nmim]Br < T-2[C_nmim]Br.T与Br^-之间的氢键作用与咪唑阳离子伴随弱氢键的堆积环境更有利,阳离子烷基链长影响不明显.在堆积构型中胸腺嘧啶与咪唑阳离子以π-π⁺色散吸引为主,并伴随C-H…O和C-H…π弱氢键作用,部分碱基电子转移至阳离子（π→π⁺）,其NBO分析显示稳定化能主要来自π→π^+*（ΣE_π→π+*²）轨道作用的贡献;T与Br^-之间以静电吸引为主,溴离子向胸腺嘧啶转移电子,稳定化能源于lp_Br→σ_N-H^*.     

Determination of the non-linearity parameter for liquids from optical measurements

The Science of Nature -     

Formation and cytotoxicity of a new disinfection by-product (DBP) phenazine by chloramination of water containing diphenylamine

Disinfection by-products (DBPs) in drinking water have caused worldwide concern due to their potential carcinogenic effects. The formation of phenazine from diphenylamine (DPhA) chloramination was studied and its cytotoxicities for two human cancer cells were also investigated. Phenazine was detected synchronously with the consumption of DPhA by chloramination, which further confirmed that the new DBP phenazine can be produced along with N-nitrosodiphenylamine (NDPhA) from DPhA chloramination. The formation of phenazine had a maximum molar yield with solution pH increasing from 5.0 to 9.0, with phenazine as the main product for DPhA chloramination at lower pH, but higher pH favored the formation of NDPhA. Thus, solution pH is the key factor in controlling the formation of phenazine and NDPhA. Both the initial DPhA and chloramine concentrations did not show a significant effect on the molar yields of phenazine, although increasing the chloramine concentration could speed up the reaction rate of DPhA with chloramines. The cytotoxicity assays showed that phenazine had significant cell-specific toxicity towards T24 (bladder cancer cell lines) and HepG2 (hepatic tumor cell lines) cells with IC50 values of 0.50 and 2.04 mmol/L, respectively, and T24 cells being more sensitive to phenazine than HepG2 cells. The IC50 values of phenazine, DPhA, and NDPhA for T24 cells were of the same order of magnitude and the cytotoxicity of phenazine for T24 cells was slightly lower than that of NDPhA (IC50, 0.16 mmol/L), suggesting that phenazine in drinking water may have an adverse effect on human health.     

Songs of two starling species: common traits versus adaptations to the social environment

We analysed, for the first time, songs of the African Red-winged Starling Onychognathus morio and compared their general characteristics with those of the European Starling Sturnus vulgaris. Both species are gregarious during the non-breeding season, but European Starlings tend to nest in colonies, form unstable pair-bonds and are occasionally polygynous, whereas Red-winged Starlings form long-term pair-bonds and occupy exclusive nesting territories. Red-winged Starlings produced the same basic song categories as European Starlings: warbles and whistles. These two categories appeared to be involved in similar social interactions in the two species. However, several aspects of song behaviour differed between the two species: Red-winged Starlings, breeding in isolated nests, preferentially used whistles for long-distance communication and showed a simpler organization of warbling song. Whistles in the Red-winged Starling were mostly shared between birds and, in contrast to the European Starling, were not indicators of individual identity. Also in contrast to the European Starling, female song in Red-winged Starlings appeared very important throughout the breeding period. Our results suggest that some song characteristics in the two species are phylogenetically conserved whereas others are affected by the distinct social systems of the two species.     

Comparative mammalian cell cytotoxicity of wastewater with elevated bromide and iodide after chlorination, chloramination, or ozonation

Recycling wastewater is becoming more common as communities around the world try to better control their water resources against an increased frequency of either prolonged droughts or intense flooding. For communities in coastal areas, wastewaters may contain elevated levels of bromide(Br~-) and iodide(I~-) from seawater intrusion or high mineral content of source waters. Disinfection of such wastewater is mandatory to prevent the spread of pathogens, however little is known about the toxicity of wastewater after disinfection in the presence of Br~-and I~-. In this study we compared the induction of chronic cytotoxicity in mammalian cells in samples of municipal secondary wastewater effluent amended with elevated levels of Br~-/I~-after disinfection by chlorine, chloramines or ozone to identify which disinfection process generated wastewater with the lowest level of adverse biological response. Chlorination increased mammalian cell cytotoxicity by 5times as compared to non-disinfected controls. Chloramination produced disinfected wastewater that expressed 6.3 times more cytotoxicity than the non-disinfected controls and was 1.3 times more cytotoxic than the chlorinated samples. Ozonation produced wastewater with cytotoxicity comparable to the non-disinfected controls and was at least 4times less cytotoxic than the chlorine disinfected wastewaters. These results indicate that compared to chlorination and chloramination, ozonation of wastewater with high Br~-/Ilevels yielded the lowest mammalian cell cytotoxicity, suggesting its potential as a more favorable method to disinfect wastewater with minimizing the biological toxicity in mind.     

Formation of iodo-trihalomethanes, iodo-haloacetic acids, and haloacetaldehydes during chlorination and chloramination of iodine containing waters in laboratory controlled reactions

Iodine containing disinfection by-products (I-DBPs) and haloacetaldehydes (HALs) are emerging disinfection by-product (DBP) classes of concern. The former due to its increased potential toxicity and the latter because it was found to be the third most relevant DBP class in mass in a U.S. nationwide drinking water study. These DBP classes have been scarcely investigated, and this work was performed to further explore their formation in drinking water under chlorination and chloramination scenarios. In order to do this, iodo-trihalomethanes (I-THMs), iodo-haloacetic acids (I-HAAs) and selected HALs (mono-HALs and di-HALs species, including iodoacetaldehyde) were investigated in DBP mixtures generated after chlorination and chloramination of different water matrices containing different levels of bromide and iodide in laboratory controlled reactions. Results confirmed the enhancement of I-DBP formation in the presence of monochloramine. While I-THMs and I-HAAs contributed almost equally to total I-DBP concentrations in chlorinated water, I-THMs contributed the most to total I-DBP levels in the case of chloraminated water. The most abundant and common I-THM species generated were bromochloroiodomethane, dichloroiodomethane, and chlorodiiodomethane. Iodoacetic acid and chloroiodoacetic acid contributed the most to the total I-HAA concentrations measured in the investigated disinfected water. As for the studied HALs, dihalogenated species were the compounds that predominantly formed under both investigated treatments.