UV/PAA降解氟甲喹污染水体的机制研究——pH影响、pH等组分相关性评价和脱氟性能分析

氟喹诺酮类抗生素应用广泛,基于其存在的环境生态风险,该类药物受到人们的重点关注.本研究采用紫外光活化过氧乙酸(UV/PAA)并用于不同pH氟甲喹(FLU)污染水体的降解.结果发现,在过氧乙酸(PAA)投加量为2 mg·L^-1时,UV/PAA对FLU具有优异的降解活性,此时FLU的反应速率常数比单独UV降解和单独PAA降解分别提升7.09和7.27倍.酸性环境有利于FLU的降解,酸性实验条件下FLU的降解率均可以达到80.0%以上,·OH在其中起主要作用;随着pH升高,FLU的降解率逐渐降低.FLU在体系中会发生脱氟降解;经过组分相关性分析发现,pH与FLU的降解速率常数k(|r|=0.96>0.5)、·OH浓度(|r|=0.91>0.5)和脱氟量(|r|=0.95>0.5)都呈显著负相关;而降解速率常数k、·OH浓度和脱氟性能两两之间具有显著的正相关关系.UV/PAA对FLU的矿化效果良好,反应30 min内FLU的荧光特征峰基本消失.经LC-MS/MS技术鉴定,FLU可能的降解途径包括：喹诺酮环开环、脱氟和脱羰等反应,降解途径有利于毒性的降低....     

克雷伯氏菌NY1产絮凝剂的阳离子修饰研究

为简化微生物絮凝剂投加步骤,消除由于助凝剂添加而引起的环境二次污染问题,以3-氯-2-羟丙基三甲基氯化铵(CTA)修饰荷负电的微生物絮凝剂(~-54mV),从而获得荷正电的改性絮凝剂.实验结果显示,CTA与NaOH的摩尔比值是影响阳离子修饰效果的主要因素;阳离子修饰的的最佳条件为:10g微生物絮凝剂, 0.015mol CTA,20%含水率,CTA与NaOH的摩尔比为0.95,80℃反应2h后.在最佳条件下所得阳离子化微生物絮凝剂的Zeta电位可达+16mV,其对高岭土的絮凝率也由阳离子化前的60.5%上升至91%.由阳离子化絮凝剂的结构表征可知,阳离子修饰过程并未改变微生物絮凝剂的根本结构,只是在原微生物絮凝剂基础上引入阳离子基团,从而增加了絮凝剂整体分子量;同时,由于阳离子基团的大量引入,絮凝剂的结晶度增加,从而使其溶解度增加.将阳离子化前后微生物絮凝剂应用于去除铜绿微囊藻,当阳离子化后微生物絮凝剂添加量为40mg/L时,其对藻类的去除率超过98%;而未阳离子修饰的微生物絮凝剂对该藻几乎没有去除效果.     

稀土掺杂钨钼酸盐类荧光粉水热法合成及结构与性能的研究

利用水热法制备了A0.925（MoO4）0.5（WO4）0.5∶Dy03.＋05（A=Ca、Sr、Ba）固溶体微晶。通过X射线衍射（XRD）、扫描电镜（SEM）、荧光分析（FA）等测试手段对微晶结构、形貌和发光性能进行了表征。结果表明A0.925（MoO4）0.5（WO4）0.5∶Dy03＋.05（A=Ca、Sr、Ba）复合钨钼酸盐微晶均呈现典型的四方晶相白钨矿结构。荧光光谱中的480nm处的偶合双峰和575nm处的锐而强的黄发射峰,分别对应于稀土离子Dy3＋的4F9/2→6 H15/2和4F9/2→6 H13/2跃迁。其中具有球状颗粒（尺寸为0.7μm）形貌的Ca0.925（MoO4）0.5（WO4）0.5∶Dy03.＋05微晶的发射峰强度最强,在光学材料中具有潜在应用。     

高分子重金属絮凝剂ISXA与ISX除浊、除Ni2+性能的比较研究

以交联淀粉、丙烯酰胺、CS2、NaOH等为原料,在一定条件下合成了一种新型高分子重金属絮凝剂不溶性淀粉黄原酸酯-丙烯酰胺接枝共聚物(ISXA).比较了它与不溶性淀粉黄原酸酯(ISX)的除浊、除Ni2 性能,探讨了各自的作用机理,并研究了几个影响ISXA和ISX去除水中浊度和Ni2 的因素.结果表明:1)在各种条件下,ISXA的除浊、除Ni2 性能均优于ISX;2)ISXA和ISX的投加量均为250mg·L-1时,Ni2 的去除率分别达到97%和87%;3)原水pH值对絮凝剂的除Ni2 效果有影响;4)在致浊物质和金属离子共同存在的水体中,两者会相互促进彼此的去除,Ni2 的去除率可达99%以上,浊度去除率提高10%左右;5)反应时间越长,处理效果越好,12min以后结果趋于平缓.     

Effects of humic acid fractions with different polarities on photodegradation of 2, 4-D in aqueous environments

Four fractions (A, B, C, and D) of humic acids (HAs) were separated based on the polarity from weak to strong. UV-vis absorption and Fourier transform infrared spectroscopy (FTIR) analysis show that the fractions C and Dpossessedmore aromatic C=C content. The influences of HAs and their fractions on the photolysis were investigated by the photodegradation of 2,4-D solutions under simulated solar light irradiation. The degradation rate of 2,4-D was found to decrease in the presence of bulk HAs or their fractions especially at high HAs concentration. The fractions of strong polarity C and D retarded the degradation rate more than the fractions of weak polarity A and B. This could be attributed to the different absorption intensity of the four HAs fractions in the order of D ⩾ C > A > B, and the stronger π-π electron donor-acceptor interactions between the strong polar fractions and 2,4-D.     

聚合氯化铝-腐殖酸(PACl-HA)絮体的物理与分形特征研究

采用低温急速冷冻-真空干燥技术制备了PACl-HA絮体的粉末样品,研究了这些样品的物理与分形特征.结果表明,PACl-HA絮体具有无定形结构,主要组成元素为C、O、Al,所含特征官能团保留了絮体组成原料的一些特征;絮体的BET比表面积为130～161 m²·g^-1,BJH累积吸附孔体积为0.38～0.52 cm³·g^-1,BJH脱附平均孔径为7.7～9.6nm,PSD峰值对应孔径8.4～11.2nm.PACl-HA絮体具有自相似性的粗糙表面,呈现多尺度分形特征;图象法和N₂吸附/脱附等温线法确定的表面分形维数Ds分别为2.03～2.26、2.24～2.37,前者的分形尺度大约处于23～390nm之间,主要属于絮体外表面尺度,而后者的分形特征尺度区间的下限大约为0.2nm,属于孔表面尺度;另外,对同一絮体,N₂吸附法和脱附法确定的孔表面分形维数不同.热力学模型计算出的D_s远大于3,与Sahouli等的研究不符.     

Photo-induced transformations of Hg(Ⅱ) species in the presence of Nitzschia hantzschiana,ferric ion,and humic acid

Effects of algae Nitzschia hantzschiana, Fe(Ⅲ) ions, humic acid, and pH on the photochemical reduction of Hg(Ⅱ) using the irradiation of metal halide lamps (λ 365 nm, 250 W) were investigated. The photoreduction rate of Hg(Ⅱ) was found to increase with increasing concentrations of algae, Fe(Ⅲ) ions, and humic acid. Alteration of pH value affected the photoreduction of Hg(Ⅱ) in aqueous solution with or without algae. The photoreduction rate of Hg(II) decreased with increasing initial Hg(Ⅱ) concentration in aqueous solution in the presence of algae. The photochemical kinetics of initial Hg(Ⅱ) and algae concentrations on the photoreduction of Hg(Ⅱ) were studied at pH 7.0. The study on the total Hg mass balance in terms of photochemical process revealed that more than 42% of Hg(Ⅱ) from the algal suspension was reduced to volatile metallic Hg under the conditions investigated.     

苦杏仁酸、苹果酸、乳酸对Cr(VI)还原作用的比较

不同温度和pH条件下,通过批式试验研究了苦杏仁酸、苹果酸、乳酸还原Cr(Ⅵ)的反应速率.结果表明,这3种α-OH酸还原Cr(Ⅵ)的能力表现为:苦杏仁酸＞苹果酸＞乳酸.苦杏仁酸对Cr(Ⅵ)的还原作用受pH变化的影响较大,而乳酸受温度变化的影响较大.同时研究了Mn(Ⅱ)对3种α-OH酸还原Cr(Ⅵ)反应速率的影响.结果表明,Mn(Ⅱ)对3种α-OH酸还原Cr(Ⅵ)均有催化作用,其中对苦杏仁酸表现更为明显.     

苦杏仁酸、苹果酸、乳酸对Cr(VI)还原作用的比较

不同温度和pH条件下,通过批式试验研究了苦杏仁酸、苹果酸、乳酸还原Cr(VI)的反应速率.结果表明,这3种α-OH酸还原Cr(VI)的能力表现为:苦杏仁酸>苹果酸>乳酸.苦杏仁酸对Cr(VI)的还原作用受pH变化的影响较大,而乳酸受温度变化的影响较大.同时研究了Mn(II)对3种α-OH酸还原Cr(VI)反应速率的影响.结果表明,Mn(II)对3种α-OH酸还原Cr(VI)均有催化作用,其中对苦杏仁酸表现更为明显.     

Response of peroxidase and catalase to acid rain stress during seed germination of rice, wheat, and rape

Seed germination of plants with various acid-resistance display different responses to acid rain. To understand the reason why such differences occur, the effects of simulated acid rain (pH 2.5–5.0) on the activities of peroxidase (POD) and catalase (CAT) during seed germination of rice (O. sativa), wheat (T. aestivum), and rape (B. chinensis var. oleifera) were investigated. Results indicated that the maximum change in activities of CAT and POD by acid rain treatment with different acidity and time in relation to the referent treatment without acid rain, was in the order: rice (28.8%, 31.7%) < wheat (34.7%, 48.3%) < rape (79.3%, 50.0%). The pH level for which the treatment with acid rain did not cause significant difference (p < 0.05) was in the order: rice (3.5).wheat (4.0).rape (5.0). Moreover, the change in activity of POD was higher than that of CAT, which showed that POD was more sensitive to acid rain stress than CAT. The difference in the ability of POD and CAT in removing free radicals was one reason why the germination indexes of these three species behaved differently. __________ Translated from Environmental Science, 2005, 26(6): 123–125 [译自: 环境科学]     

Formation mechanisms of nitrous acid (HONO) during the haze and non-haze periods in Beijing, China

As an important precursor of hydroxyl radical (OH), nitrous acid (HONO) plays a significant role in atmospheric chemistry. Here, an observation of HONO and relevant air pollutants in an urban site of Beijing from 14 to 28 April, 2017 was performed. Two distinct peaks of HONO concentrations occurred during the observation. In contrast, the concentration of particulate matter in the first period (period Ⅰ) was significantly higher than that in the second period (period Ⅱ). Comparing to HONO sources in the two periods, we found that the direct vehicle emission was an essential source of the ambient HONO during both periods at night, especially in period Ⅱ. The heterogeneous reaction of NO₂ was the dominant source in period Ⅰ, while the homogeneous reaction of NO with OH was more critical source at night in period Ⅱ. In the daytime, the heterogeneous reaction of NO₂ was a significant source and was confirmed by the good correlation coefficients (R²) between the unknown sources (P_unknown) with NO₂, PM_2.5, NO₂ × PM_2.5 in period Ⅰ. Moreover, when solar radiation and OH radicals were considered to explore unknown sources in the daytime, the enhanced correlation of P_unknown with photolysis rate of NO₂ and OH ($J_{{\mathrm{NO}}_2}$ × OH) were 0.93 in period Ⅰ, 0.95 in period Ⅱ. These excellent correlation coefficients suggested that the unknown sources released HONO highly related to the solar radiation and the variation of OH radicals.     

全氟辛酸在紫贻贝体内的富集、分布与消除

以紫贻贝为受试生物,采用半静态暴露的方式,研究了全氟辛酸（PFOA）在紫贻贝体内的富集特征、器官分布与消除规律.结果表明,紫贻贝可快速富集PFOA,整贝在不同浓度PFOA暴露下,于4~6d达到平衡态,半衰期为0.34~0.44d（约8~10h）,生物富集系数（BCFs）为5.10~9.55mL/g.PFOA在紫贻贝鳃和内脏团中的富集作用大于外套膜、性腺和闭壳肌.紫贻贝中PFOA的含量在净化6~9d后趋于空白组水平,主要代谢途径可能为鳃的作用.紫贻贝对PFOA的富集作用与暴露浓度相关,浓度越低,吸收系数和生物富集系数越大.     

重金属汞对土壤酸性磷酸酶的影响及其机理

通过土壤培养试验、紫外吸收光谱和荧光光谱技术 ,研究了重金属汞对土壤酸性磷酸酶催化活性、动力学性质的影响及机理 .结果表明 ,汞对土壤酸性磷酸酶活性、酶促反应动力学性质均具有显著影响 .汞对土壤酸性磷酸酶的作用可能为非竞争与反竞争混合的抑制类型 .而汞对麦芽酸性磷酸酶的抑制作用为反竞争性抑制 .重金属汞通过改变土壤酸性磷酸酶分子色氨酸、酪氨酸残基的微环境致使酶活性中心的构象发生变化 ,进而对酶的催化活性产生影响     

O2、NO-3、NO-2为电子受体的生物除磷比较

通过平行运行3个分别以O₂、NO^-₃、NO^-₂为电子受体的SBR除磷系统,探讨了反硝化除磷区别于好氧除磷的工艺特征及其内在微生物竞争机制.NO^-₂不会对经驯化后反硝化聚磷菌（DPAO）的缺氧吸磷产生直接抑制作用,但其作为反硝化除磷电子受体的效能远低于NO^-₃;具备利用NO^-₃而缺乏NO^-₂反硝化酶系的DPAO（DPAO₅）流失及聚糖菌（GAO）增殖是根本原因.而NO^-₃是一种高效电子受体,其反硝化除磷效能与以O₂为受体的好氧除磷系统相当,两者在除磷计量学和功能菌群构成上十分接近.作为聚磷菌（PAO）的竞争者,GAO在3个研究系统中均大量存在.基于对不同电子受体的利用能力,PAO包含P_O、P_N、P_n、P_Nn、P_ON、P_ONn等6个种类.P_ON和P_ONn等兼性PAO是生物除磷的主体,其在污泥中比例越高,系统的除磷负荷也越大,即SBR_o＞SBR_n5＞SBR_n3.