自来水给水系统中有机磷酸酯的污染特征及健康风险评价

有机磷酸酯(OPEs)是一种新兴有机污染物,其作为阻燃剂得到了广泛应用,并且在环境介质中普遍检出,但其在自来水系统中的污染特征及饮用水摄人所引起的健康风险鲜有报道.以天津市某自来水处理厂为例,采集了进水-各处理工艺出水-清水池出水-管网末梢水4个季节的水样,分析了13种OPEs的污染特征及其随季节的变化趋势,并评估了饮...     

Optimization of the T3-induced Xenopus metamorphosis assay for detecting thyroid hormone signaling disruption of chemicals

T3-induced Xenopus metamorphosis is an ideal model for detecting thyroid hormone(TH)signaling disruption of chemicals. To optimize the T3-induced Xenopus assay and improve its sensitivity and reproducibility, we intend to develop quantitatively morphological endpoints and choose appropriate concentrations and exposure durations for T3 induction.Xenopus laevis at stage 52 were exposed to series of concentrations of T3(0.31–2.5 nmol/L)for 6 days. By comparing morphological changes induced by T3, we propose head area,mouth width, unilateral brain width/brain length, and hindlimb length/snout-vent length as quantitative parameters for characterizing T3-induced morphological changes, with body weight as a parameter for indicating integrated changes. By analyzing time-response curves, we found that following 4-day exposure, T3-induced grossly morphological changes displayed linear concentration–response curves, with moderate morphological changes resulting from 1.25 nmol/L T3 exposure. When using grossly morphological endpoints to detect TH signaling disruption, we propose 4 days as exposure duration of T3, with concentrations close to 1.25 nmol/L as induction concentrations. However, it is appropriate to examine morphological and molecular changes of the intestine on day 2 due to their early response to T3. The quantitative endpoints and T3 induction concentrations and durations we determined would improve the sensitivity and the reproducibility of the T3-induced Xenopus metamorphosis assay.     

A2O小试系统与实际工艺单元中OPEs去除的比较

污水处理厂出水是环境中OPEs的重要来源,且污水处理厂的生物处理单元可去除部分OPEs.为了更好的研究污水处理厂工况条件,以达到优化去除宏量有机物和微量有机物的目的,良好的小试装置必不可少.本研究在实验室设计并安装了一套A²O小试装置,根据有机磷酸酯的结构特点,在进水中投加了3种代表性的有机磷酸酯.比较了小试装置中与实际工艺单元中这3种有机磷酸酯的去除规律,发现OPEs在A²O小试中的去除规律与实际工艺单元中相似,磷酸三丁氧酯（TBEP）在两种工况下去除效果均较好,总去除率分别为84.6%与83.6%,磷酸三（1-氯-2-丙基）酯（TCPP）去除效果均较差.在不同处理单元中,由于厌氧池中主要发生水解作用,TCPP在两种工况下的厌氧池中都可去除,且在A²O小试厌氧池中的去除率（57.7%）优于实际工艺（25.5%）.TBEP的去除主要发生在好氧池中,且A²O小试二沉池可以有效去除TBEP（67.9%）,优于实际工艺的二沉池.两种工况下,好氧池曝气强度较大,引入磷酸三（1-氯-2-丙基）酯（TCPP）不易降解,TCPP在好氧池去除效果较差.除此之外,优化了小试装置的OPEs的检测取样量保证检测的准确性.     

花生对土壤中邻苯二甲酸酯的吸收累积特征

选择邻苯二甲酸二丁酯(Dibutyl phthalate,DBP)和邻苯二甲酸二(2-乙基己基)酯(di-(2-ethylhexyl)phthalate,DEHP)作为目标污染物,通过盆栽试验研究花生(Arachis hypogaea)对土壤中邻苯二甲酸酯的吸收累积特征.结果表明:邻苯二甲酸酯污染对青花7号花生生物量无显著影响,而青花5号花生生物量则显著降低,在污染水平I(40 mg·kg-1)和污染水平II(80 mg·kg-1)下花生籽粒产量分别减少24.11%和48.75%.随着土壤中邻苯二甲酸酯污染水平的增高,花生植株各部位的DBP和DEHP含量均呈显著升高趋势,花生根系DBP和DEHP含量显著高于其它部位.在2个污染水平下,花生籽粒对DBP和DEHP的富集量占植株富集总量的比例最高.花生种植后土壤中邻苯二甲酸酯残留量均有所降低,在相同的污染水平下DEHP残留量显著高于DBP.花生籽粒对DBP的富集系数高于DEHP的生物富集系数,分别介于0.50~1.87和0.53~0.98之间.     

In vitro evaluation of inorganic and methyl mercury mediated cytotoxic effect on neural cells derived from different animal species

To extend the current understanding of the mercury-mediated cytotoxic effect,five neural cell lines established from different animal species were comparatively analyzed using three different endpoint bioassays:thiazolyl blue tetrazolium bromide,3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide assay(MTT),neutral red uptake assay(NRU),and Coomassie blue assay(CB).Following a 24-hr exposure to selected concentrations of mercury chloride(HgCl_2) and methylmercury(Ⅱ) chloride(MeHgCl),the cytotoxic effect on test cells was characterized by comparing their 50%inhibition concentration(IC_(50)) values.Experimental results indicated that both these forms of mercury were toxic to all the neural cells,but at very different degrees.The IC_(50)values of MeHgCl among these cell lines ranged from 1.15±0.22 to 10.31 ± 0.70 μmol/L while the IC_(50) values for HgCl_2 were much higher,ranging from 6.44 ± 0.36 to 160.97±19.63 μmol/L,indicating the more toxic nature of MeHgCl.The IC_(50) ratio between HgCl_2and MeHgCl ranged from 1.75 to 96.0,which confirms that organic mercury is much more toxic to these neural cells than inorganic mercury.Among these cell lines,HGST-BR and TriG44 derived from marine sea turtles showed a significantly high tolerance to HgCl_2 as compared to the three mammalian neural cells.Among these neural cells,SK-N-SH represented the most sensitive cells to both chemical forms of mercury.     

Assessment of antimicrobial activity of Catechu and its dyed substrate

The present study was undertaken to evaluate the antimicrobial activity of catechu in solution and % microbial reduction of dyed wool samples against Escherichia coli MTCC 443, Staphylococcus aureus MTCC 902, Candida albicans ATCC 10261 and Candida tropicalis ATCC 750, by using micro-broth dilution method, disc diffusion assay and growth curve studies. The dye showed the maximum antimicrobial activity at 20% w/v, inhibiting the microbial growth by more than 90%. In the next set of the experiments the antimicrobial activity of the dye was compared on woollen yarn alone and on pre-mordanted samples. The reduction in antimicrobial activity was observed when mordanted samples were examined. K/S, CIELab values and fastness properties of the dyed samples were assessed. The structural morphology of woollen yarn was also evaluated using scanning electron microscopy (SEM). Haemolytic activity on human erythrocytes was studied to exclude possibility of further associated cytotoxicity. The observed antimicrobial characteristics and negligible cytoxicity of catechu indicate that the dye might be a promising antimicrobial agent for developing bioactive textile materials and clothing.     

Determination of estrogenic activity in the river Chienti (Marche Region, Italy) by using in vivo and in vitro bioassays

Environmental estrogen-like compounds (i.e. xenoestrogens) are a variety of pollutants, ranging from synthetic to natural occurring molecules, that are found in surface and waste waters over a wide range of concentrations. In aquatic environment, the overall estrogenic activity is often due to the presence of a mixture of chemicals and their degraded products which can induce synergistic effects. Current strategies for monitoring estrogen-like chemicals are based on the use of a battery of in vivo and in vitro ecotoxicological tests. In this regard, the aim of the present work was to carry out a bio-monitoring study for testing estrogenicity of the Chienti river (Marche Region, Italy) by using both an E-screen and a vitellogenin (Vtg) induction assay in juvenile goldfish. Three sites were used for analysis, localized at the mouth (sampling point 1), in the middle (sampling point 2) and at the origin (sampling point 3) of Chienti river. For most of the water samples (i.e. samples collected at sampling points 2 and 3), clear estrogenic activity was detected in the E-screen assay suggesting different proliferation activities in function of the collecting site. In contrast, the Vtg ELISA demonstrated that water samples collected from each sampling point were estrogenic. Overall, we showed for the first time that the estrogenic activities in water samples from the Chienti river were significant in both in vivo and in vitro; we also observed a different sensitivity between bioassays.     

Re-evaluation of thyroid hormone signaling antagonism of tetrabromobisphenol A for validating the T3-induced Xenopus metamorphosis assay

We developed the T3-induced Xenopus metamorphosis assay, which is supposed to be able to sensitively detect thyroid hormone(TH) signaling disruption of chemicals. The present study aimed to validate the T3-induced Xenopus metamorphosis assay by re-evaluating the TH signaling antagonism of tetrabromobisphenol A(TBBPA), a known TH signaling disruptor. According to the assay we developed, Xenopus tadpoles at stage 52 were exposed to 10–500 nmol/L TBBPA in the presence of 1 nmol/L T3. After 96 hr of exposure, TBBPA in the range of 10–500 nmol/L was found to significantly inhibit T3-induced morphological changes of Xenopus tadpoles in a concentration-dependent manner in term of body weight and four morphological endpoints including head area(HA), mouth width(MW), unilateral brain width/brain length(ULBW/BL), and hind-limb length/snout-vent length(HLL/SVL).The results show that these endpoints we developed are sensitive for characterizing the antagonistic effects of TBBPA on T3-induced metamorphosis. Following a 24-hr exposure,we found that TBBPA antagonized expression of T3-induced TH-response genes in the tail,which is consistent with previous findings in the intestine. We propose that the tail can be used as an alternative tissue to the intestine for examining molecular endpoints for evaluating TH signaling disruption. In conclusion, our results demonstrate that the T3-induced Xenopus metamorphosis assay we developed is an ideal in vivo assay for detecting TH signaling disruption.     

Mn-Ce-Co/TiO2催化剂低温脱硝活性研究

以纳米TiO2为载体,通过浸渍法制备一系列改性Mn-Ce/TiO2脱硝催化剂.通过实验考察不同元素组分催化剂的脱硝活性,同时探讨金属氧化物掺杂对提高催化剂低温脱硝活性的机理.活性测试结果显示,Co掺杂能最有效地提高Mn-Ce/TiO2催化剂在低温段的SCR脱硝活性,在n(Co):n(TiO2)=0.08～0.10、体积空速为35100h-1的条件下,催化剂在120℃时就能达到80%以上的NO去除率,140℃左右时的NO去除率接近100%.BET、XRD、TPR、TPD等表征测试结果表明,Co掺杂可改进Mn-Ce/TiO2催化剂的物化特性,增加催化剂表面的活性酸位点及活性氧数量,提高催化剂的氧化还原能力,从而提高Mn-Ce/TiO2催化剂低温SCR脱硝活性.     

水体悬浮颗粒物对斜生栅藻生理生化及光合活性的影响

通过研究不同浓度(30、40、50、60、70 mg·L-1)和不同粒径(0～75μm、75 ～ 96μm、96 ～150 μm、150～ 250 μm)水体悬浮颗粒物对斜生栅藻(Scenedesmus obliquus)叶绿素a含量、抗氧化系酶活性、脂质过氧化物丙二醛(MDA)含量、可溶性蛋白含量及光合参数变化的影响,探讨了水体悬浮颗粒物对斜生栅藻生理生化及光合活性影响的机制.结果表明,预处理与未处理悬浮颗粒物在一定浓度范围内会促进藻类生长,超过各自临界浓度(预处理为40 mg·L-1、未处理为50 mg·L-1)后,随着颗粒物浓度的增加会对藻类生长产生抑制现象未经处理的相同浓度不同粒径颗粒物对斜生栅藻都表现出抑制作用,0～75μm粒径组颗粒物作用下藻体内超氧化物歧化酶(SOD)、过氧化氢酶(CAT)、MDA和可溶性蛋白质含量等均显著区别于其他粒径组的作用(p＜0.05).经过预处理的相同浓度不同粒径颗粒物中,96～150μm粒径组对藻类的生长抑制较其他粒径组明显,且小粒径组颗粒物对藻类体内SOD、CAT、MDA和可溶性蛋白质含量等影响较大.受不同浓度悬浮颗粒物胁迫的斜生栅藻相对电子传递速率随着时间延长在一定程度上降低,但这种抑制作用在藻细胞的耐受范围,藻细胞可以通过自身调节将电子传递速率恢复到正常水平甚至更高以抵抗逆境环境.     

Antimicrobial activity of silver loaded MnO2 nanomaterials with different crystal phases against Escherichia coli

Silver-loaded MnO_2 nanomaterials(Ag/MnO_2),including Ag/α-MnO_2,Ag/β-MnO_2,Ag/γ-MnO_2and Ag/δ-MnO_2 nanorods,were prepared with hydrothermal and impregnation methods.The bactericidal activities of four types of Ag/MnO_2 nanomaterials against Escherichia coli were investigated and an inactivation mechanism involving Ag~+ and reactive oxygen species(ROS)was also proposed.The bactericidal activities of Ag/MnO_2 depended on the MnO_2 crystal phase.Among these nanomaterials,Ag/β~-MnO_2 showed the highest bactericidal activity.There was a 6-log decrease in E.coli survival number after treatment with Ag/β~-MnO_2 for120 min.The results of 5,5-dimethyl-l-pyrroline-N-oxide spin-trapping measurements by electron spin resonance indicate OH and O_2~- formation with addition of Ag/β-MnO_2,Ag/γ-MnO_2 or Ag/δ-MnO_2.The strongest peak of OH appeared for Ag/β-MnO_2,while no OH or ·O_2~-signal was found over Ag/α-MnO_2.Through analysis of electron spin resonance(ESR) and Ag+elution results,it could be deduced that the toxicity of Ag~+ eluted from Ag/MnO_2 nanomaterials and ROS played the main roles during the bactericidal process.Silver showed the highest dispersion on the surface of β-MnO_2,which promoted ROS formation and the increase of bactericidal activity.Experimental results also indicated that Ag/MnO_2 induced the production of intracellular ROS and disruption of the cell wall and cell membrane.     

Surface modification of polypropylene non-woven fibers with TiO2 nanoparticles via layer-by-layer self assembly method: Preparation and photocatalytic activity

Polypropylene (PP) meltblown fibers were coated with titanium dioxide (TiO₂) nanoparticles using layer-by-layer (LbL) deposition technique. The fibers were first modified with 3 layers of poly(4-styrenesulfonic acid) (PSS) and poly(diallyl-dimethylammonium chloride) (PDADMAC) to improve the anchoring of the TiO₂ nanoparticle clusters. PDADMAC, which is positively charged, was then used as counter polyelectrolyte in tandem with anionic TiO₂ nanoparticles to construct TiO₂/PDADMAC bilayer in the LbL fashion. The number of deposited TiO₂/PDADMAC layers was varied from 1 to 7 bilayer, and could be used to adjust TiO₂ loading. The LbL technique showed higher TiO₂ loading efficiency than the impregnation approach. The modified fibers were tested for their photocatalytic activity against a model dye, Methylene Blue (MB). Results showed that the TiO₂ modified fibers exhibited excellent photocatalytic activity efficiency similar to that of TiO₂ powder dispersed in solution. The deposition of TiO₂ 3 bilayer on the PP substrate was sufficient to produce nanocomposite fibers that could bleach the MB solution in less than 4 hr. TiO₂-LbL constructions also preserved TiO₂ adhesion on substrate surface after 1 cycle of photocatalytic test. Successive photocatalytic test showed decline in MB reduction rate with loss of TiO₂ particles from the substrate outer surface. However, even in the third cycle, the TiO₂ modified fibers are still moderately effective as it could remove more than 95% of MB after 8 hr of treatment.     

重金属铅、铬胁迫对斜生栅藻的生长、光合性能及抗氧化系统的影响

以斜生栅藻(Scenedesmus obliquus JNU49)为研究对象,研究了重金属Pb2+、Cr3+、Cr6+对斜生栅藻生物量积累、光合性能及抗氧化系统的影响.结果表明,Pb2+、Cr3+、Cr6+对斜生栅藻的半数抑制浓度(IC50)分别为82.94、121.15、23.65μmol·L-1.半数抑制浓度胁迫下,斜生栅藻的放氧速率分别在第2~8 d(Pb2+胁迫)、1~3 d(Cr3+、Cr6+胁迫)受到明显抑制,而呼吸速率无明显变化;Pb2+胁迫下,斜生栅藻光系统Ⅱ(PSⅡ)的原初光能转化效率(Fv/Fm)、实际光能转化效率(Yield)、相对电子传递速率(rETR)均明显低于对照,光化学淬灭(qP)从第1~5 d高于对照,而第6~8 d则显著低于对照;Cr3+和Cr6+胁迫对斜生栅藻光合性能的影响不如Pb2+胁迫明显.斜生栅藻丙二醛(MDA)含量在重金属胁迫下变高,以第3、4 d尤为明显;超氧化物歧化酶(SOD)活性升高,于第3、4 d较为明显;过氧化氢酶(CAT)活性、总抗氧化活性(T-AOC)在重金属胁迫下均小幅度提升.通过本研究发现,斜生栅藻的生物量、光合速率、叶绿素荧光参数和SOD活性等指标对重金属胁迫的反应均较为灵敏,可作为评估重金属胁迫对微藻危害的指标.     

铅与丁草胺的交互作用对油麦菜生长和抗氧化酶活性的影响

盆栽土培试验研究了重金属铅与除草剂丁草胺的复合污染对油麦菜生长及生理生化的毒性效应.结果表明土壤铅浓度小于500mg.kg-1对油麦菜发芽率的影响不明显,铅浓度为150mg.kg-1对油麦菜株高有促进作用,但对叶片过氧化物酶（POD）和过氧化氢酶（CAT）活性有明显抑制作用.土壤铅浓度为500mg.kg-1时,油麦菜根...