单偶氮染料AY17的光催化降解动力学及机制

为了研究水体环境中单偶氮染料酸性黄17(AY17)有效地去除方式及其可能的降解途径、转化和归趋等,实验首先探索了AY17在不同深度氧化体系中降解的可行性,研究发现其去除效率的大小按照UV/H_2O_2UV/Na_2S_2O_8≈UV/FeSO_4·7H_2OUV/KHSO_5UV/TiO_2排列.然后选取UV/TiO_2体系,研究了催化剂用量,反应温度,底物浓度以及溶液初始p H值等因素对其光催化降解动力学的影响,结果表明AY17的光催化降解遵循假一级动力学,其降解速率常数为0.011 2 min~(-1);当催化剂TiO_2用量为3 g·L~(-1)时其降解效果最好;高温有利于AY17的光催化降解,而随着底物浓度和溶液初始p H值的升高,其降解速率常数显著下降.最后利用GC/MS对AY17光催化降解中间产物进行了初步鉴定,研究发现在·OH等活性氧物种的作用下偶氮键的断裂、羟基自由基对芳香环上基团的取代以及吡唑环的裂解是其主要降解途径.     

雌二醇在土壤/沉积物中的吸附特征及猪粪DOM对吸附的影响

天然类固醇雌激素如17β-雌二醇(E2)在极低质量浓度下(ng.L-1)即可干扰水生生物的生殖功能.为准确预测E2向水体迁移,通过摇床实验研究了E2在中国北方3种不同土壤/沉积物表面的吸附特征,同时探讨了猪粪及其堆肥可溶态有机质(DOM)对E2吸附的影响.结果发现,E2在土壤/沉积物表面吸附符合Freundlich等温吸附方程(R2>0.76),E2在河流沉积物、潮土、黑土皆表现为非线性,其中黑土吸附的非线性最强(n=0.74);吸附系数Kf介于26.2～57.5,并与有机质含量呈显著正相关(P<0.05).猪粪及其堆肥DOM显著抑制E2在土壤/沉积物表面的吸附,其中堆肥DOM的影响尤为显著.研究认为,有机质是土壤/沉积物中吸附E2的主要组分,共存猪粪DOM在较低浓度下可提高E2迁移性,增加E2向地表和地下水的迁移风险.     

Forecasting iron ore import and consumption of China using grey model optimized by particle swarm optimization algorithm

The iron and steel industry plays a fundamental role in a country's national economy, especially in developing countries. China is the largest iron ore consumption market in the world. However, because of limited domestic iron ore resources, a large proportion of iron ore is imported from other countries. Faced with the conflict between the iron ore supply shortage and the growing demand, it is necessary for the government to predict imports and total consumption. This paper develops a high-precision hybrid model based on grey prediction and rolling mechanism optimized by particle swarm optimization algorithm. We use the China Statistical Yearbook (1996–2011) as our database to test the efficiency and accuracy of the proposed method. According to the experimental results, the proposed new method clearly can improve the prediction accuracy of the original grey model. Future projections have also been done for iron ore imports and total consumption in China in the next five years.     

Prenatal diagnosis of charcot-marie-tooth disease type 1a (CMT1A) using molecular genetic techniques

Charcot-Marie-Tooth disease type 1A (CMT1A) is a frequent hereditary motor and sensory neuropathy of the peripheral nerves. In most cases, the disease is associated with a 1.5 Mb tandem duplication at 17p11.2. A 42-year-old pregnant woman requested prenatal diagnosis because of her age and since both her husband and two children were severely affected with CMT1. The CMT1A duplication was demonstrated in the father's, the two children's, and the fetus's DNA using different molecular genetic methods. Although cytogenetical analysis showed a normal female karyotype in the fetus, the parents decided to terminate the pregnancy because of the genetic risk associated with the CMT1A duplication.     

Differential response of multiple zebrafish hepatic F-box protein genes to 17α-ethinylestradiol treatment

Estrogens are accumulating in environment and their e ects on a variety of reproductive processes and tumorigenesis were reported by previous study, but the mechanism of estrogen promoting neoplasia was still not clear. F-box protein (FBP) is the component of E3 ubiquitin ligase which takes part in a variety of key biological processes. In this study, using mature male zebrafish, which are more sensitive to estrogen treatment, we examined influence of 17 -ethinylestradiol (EE2) exposure on the expression of a series of hepatic FBP genes, which take part in a variety of biological processes, including tumorigenesis. The influence of EE2 on the expression of hepatic mRNA concentrations of FBP genes were quantified based on the expression of the optimal internal control gene in male zebrafish after 7-day exposure to EE2, from a low-dose concentration (1 ng/L) to environmentally relevant concentrations (10, 100 ng/L). Our results showed that EE2 exposure reduced the expression of fbxl14a, fbxl14b, fbxo25 and -TRCP2b, but enchanced the expression of skp2. While the alterations in fbxl2, fbxw7, fbxo9, -TRCP2a, fbxl18 and fbxo45 mRNA levels were not observed after EE2 exposure. Thus, our results showed that the expression of hepatic FBP genes exhibited di erentially in male zebrafish exposed EE2. The changes of the expression level of FBP genes induced by EE2 may be an important clue to elucidate the correlations of estrogen and hepatic tumors.     

Methodological approach for metal pollution evaluation in sediments collected from the Taranto Gulf

The concentrations of Hg, Cd, Pb, Cu, Ni, V, and Sn were determined in marine sediments collected from Taranto Gulf (Ionian Sea, Southern Italy). The aim of this article is to study the methodological approach in order to evaluate total metal levels determined in marine sediments of a contaminated area (Taranto Gulf, Southern Italy), to identify contaminated areas and to predict adverse biological effects based on Sediment Quality Guidelines (SQGs). The results are discussed in relation to geological characteristics of sediments in order to define background levels and anthropogenic input. Experimental results were elaborated by multivariate statistical techniques and Geographical Information System (GIS) software. The geoaccumulation index I _geo and two sets of SQGs (in particular (a) the threshold effect level (TEL), the probable effect level (PEL) and (b) the effect range-low (ERL) and the effect range median (ERM)) have been used for environmental evaluation of metal concentrations. Results show that in Taranto coastal area, Mar Piccolo basin represents the most contaminated area. A comparison with results from other Mediterranean areas demonstrates that for some metals (such as Cd, Pb, and Hg) Taranto seas represent one of the most polluted areas in the Mediterranean Sea. A comparison of metal levels with SQGs also suggests an ecotoxicological risk for benthic organisms mainly in the first inlet of Mar Piccolo.     

HHMHC对Cu2+、Ni2+的萃取性能

以对羟基苯甲酸为原料,通过化学修饰合成得到上沿羧基化的杯[6]芳烃羟肟衍生物,即5,11,17,23,29,35-六羧基-37,38,39,40,41,42-六羟肟酸甲氧基杯[6]芳烃(HHMHC),采用IR对其结构性能进行表征,并探讨了溶液初始pH值、初始重金属离子(Cu2+、Ni2+)浓度、萃取时间、温度等因素对HHMHC萃取重金属离子的影响.结果表明,在温度为30℃时HHMHC萃取Ni2+和Cu2+的最佳pH值分别为5.0、6.0,萃取平衡时间均为30min.用准二级动力学模型(R2>0.99)和Freundlich等温模型(R2>0.999)均可较好的拟合其萃取过程,通过计算萃取过程的热力学参数,得到Gibbs自由能(ΔG0)和焓变(ΔH0)均小于0,表明萃取反应是一个自发的放热反应.通过红外光谱图分析和考察溶液pH值对萃取分配比的影响,探讨HHMHC萃取Cu2+、Ni2+的机理,结果表明此萃取过程除了存在阳离子交换机理外,还存在与冠醚萃取相同的离子配位萃取,参与配位作用的主要是羟肟基团(–CONHOH).     

Photosensitivity sources of dissolved organic matter from wastewater treatment plants and their mediation effect on 17α-ethinylestradiol photodegradation

● EE2 photodegradation behavior in the presence of four WWTPs’ DOM was explored. ● The ³DOM* played a major role in the EE2 photodegradation mediated by WWTPs’ DOM. ● The A²/O process DOM contained more aromatic and oxygen-containing substances. ● Possible photosensitivity sources of DOM in the A²/O process were proposed. Dissolved organic matter (DOM) from each treatment process of wastewater treatment plants (WWTPs) contains abundant photosensitive substances, which could significantly affect the photodegradation of 17α-ethinylestradiol (EE2). Nevertheless, information about EE2 photodegradation behavior mediated by DOM from diverse WWTPs and the photosensitivity sources of such DOM are inadequate. This study explored the photodegradation behavior of EE2 mediated by four typical WWTPs’ DOM solutions and investigated the photosensitivity sources of DOM in the anaerobic-anoxic-oxic (A²/O) process. The parallel factor analysis identified three varying fluorescing components of these DOM, tryptophan-like substances or protein-like substances, microbial humus-like substances, and humic-like components. The photodegradation rate constants of EE2 were positively associated with the humification degree of DOM (P < 0.05). The triplet state substances were responsible for the degradation of EE2. DOM extracted from the A²/O process, especially in the secondary treatment process had the fastest EE2 photodegradation rate compared to that of the other three processes. Four types of components (water-soluble organic matter (WSOM), extracellular polymeric substance, humic acid, and fulvic acid) were separated from the A²/O process DOM. WSOM had the highest promotion effect on EE2 photodegradation. Fulvic acid-like components and humic acid-like organic compounds in WSOM were speculated to be important photosensitivity substances that can generate triplet state substances. This research explored the physicochemical properties and photosensitive sources of DOM in WWTPs, and explained the fate of estrogens photodegradation in natural waters.     

甲醛暴露时间延长加剧小鼠哮喘模型肺氧化损伤并促进IL-17表达

为了探究不同暴露时间甲醛对小鼠哮喘模型肺氧化应激及IL-17表达的影响,用浓度为3.0 mg·m~(-3)的甲醛气体吸入染毒,同时将48只雄性Balb/c小鼠随机分为6组:(1)对照组(生理盐水组);(2)ovalbumin(OVA)致敏组;(3)0.5 h甲醛+OVA组;(4)1h甲醛+OVA组;(5)1.5 h甲醛+OVA组;(6)2 h甲醛+OVA组,以不同时间长度进行甲醛暴露,连续35 d。OVA致敏组、0.5 h甲醛+OVA组、1 h甲醛+OVA组、1.5 h甲醛+OVA组、2 h甲醛+OVA组均在第11、18及25天腹腔注射OVA致敏液(5 mg OVA+175 mg Al(OH)_3+30 mL生理盐水),第29~35天(共计1周)进行1%OVA雾化(30 min·d~(-1)),每日1次,诱发哮喘。第36天进行以下操作:取肺组织测定肺系数并制作肺匀浆,检测肺组织中活性氧自由基(ROS)、丙二醛(MDA)和还原型谷胱甘肽(GSH)的含量,并采用ELISA法检测肺组织中IL-17的水平。同时,采用HE染色法观察小鼠肺部气道的病理学变化。结果显示,在浓度为3.0 mg·m~(-3)的甲醛气体吸入染毒条件下,与对照组相比,1.5 h甲醛+OVA染毒组、2 h甲醛+OVA染毒组ROS、MDA、IL-17含量上升,具有统计学意义(P0.01)。同时,随着暴露时间长度的增加,小鼠肺部气道出现明显病理学变化。综上所述,每天2 h甲醛+OVA染毒能对小鼠肺造成损伤并恶化OVA对小鼠肺的损伤,产生炎症反应,并通过氧化应激反应介导。     

Microbial transformation of synthetic estrogen 17α-ethinylestradiol

Natural estrogens such as estrone, 17β-estradiol, estriol, and the particularly recalcitrant synthetic estrogen 17α-ethinylestradiol used as oral contraceptive, accumulate in the environment and may give rise to health problems. The processes participating in their removal from soil, wastewater, water-sediments, groundwater-aquifer material, and wastewater or sewage treatment plant effluents may involve the action of bacterial and microbial consortia, and in some cases fungi and algae. This review discusses the different efficiencies of bacterial degradation of 17α-ethinylestradiol under aerobic and anaerobic conditions, the role of sulfate-, nitrate-, and iron-reducing conditions in anaerobic degradation, and the role of sorption. The participation of autotrophic ammonia oxidizing bacteria and heterotrophic bacteria in cometabolic degradation of estrogens, the estrogen-degrading action of ligninolytic fungi and their extracellular enzymes (lignin peroxidase, manganese-dependent peroxidase, versatile peroxidase, laccase), and of algae are discussed in detail.