有机化学品不同温度下(过冷)液体蒸气压预测模型的建立与评价

(过冷)液体蒸气压(PL)是评价化学品在环境中分配、迁移和归趋行为的重要参数。PL具有较强的温度依附性。发展一种能够精确预测不同环境温度下化学品PL的方法,有助于填补化学品生态风险评估的大量数据缺失。本研究收集整理了661种有机化合物在不同温度下(200~830 K)共计10 478个log PL值。在此基础上,采用偏最小二乘(PLS)回归和支持向量机(SVM)方法,构建了PL的线性和非线性预测模型。结果表明:2种模型均具有良好的拟合度、稳健性及预测能力,SVM模型的预测性能略高于PLS模型(PLS:R2adj.tra=0.912,RMSEtra=0.477,Q2ext=0.910;SVM:R2adj.tra=0.997,RMSEtra=0.092,Q2ext=0.967)。机理分析表明,温度是影响PL的主要因素,温度越高,蒸气压越大;其次,X1sol也影响PL大小,X1sol用来描述分子间的色散作用,分子间色散力越小,蒸气压越大;此外,化合物的氢键个数、极性和分子构型等因素也影响PL大小。采用Wiliams plot方法表征了PLS模型应用域。所建立的模型可用来预测烷烃、烯烃、醇、酮、羧酸、苯、酚、联苯、卤代芳香烃、含N化合物及含S化合物在不同温度下的PL数据。     

广州地区孕妇羊水中PCBs暴露水平初步研究

随机采集广州地区非职业PCBs(polychlorinated biphenyls,多氯联苯)暴露单胎孕妇分娩时羊水,分析羊水中PCBs浓度水平;结合孕妇临床资料(年龄、孕周、身体质量指数(body mass index,BMI))以及孕妇居住环境信息等,阐明了广州地区非职业暴露孕妇羊水PCBs蓄积的影响因素。结果表明,∑33PCBs浓度为15.91-324.38 ng·g-1,平均值为114.34±83.52 ng·g-1,中值为84.8 5ng·g-1;其中十氯含量最低,平均浓度为2.66±3.46 ng·g-1,中值为1.47 ng·g-1;六氯PCBs含量最高,平均浓度为28.79±33.84 ng·g-1,中值为17.48 ng·g-1。样本中有31种PCBs同分异构体在孕妇羊水中检出,分别为PCB 8、28、30、49、52、70、74、77、82、87、99、101、105、114、118、126、128、138、153、156、158、166、169、170、179、180、183、187、189、198和209;羊水主要的PCBs暴露以五氯PCBs、六氯PCBs和七氯PCBs为主,主要的同分异构体为PCB 138(4.73%)、179(4.15%)、153(3.92%)、183(3.89%)、166(3.77%)、187(3.74%)以及180(3.67%);暴露水平与美国、西班牙、加拿大等地区相比属于严重水平。统计结果显示,年龄、身体质量指数和孕周与PCBs蓄积有显著性正相关关系;工业区居住的孕妇相与非工业区居住孕妇相比,上述统计结果更为显著。     

Fenton法和类Fenton法降解土壤中的二苯砷酸

本文对Fenton法与类Fenton法降解土壤中的二苯砷酸(diphenylarsinic acid,DPAA)进行了研究.考察了H2O2投加量和催化剂种类(Fe2+/Fe3+)对红壤及黑土中DPAA降解效果的影响,并采用高效液相色谱-质谱联用法(HPLC-MS/MS)对降解中间产物进行了初步鉴定.结果显示,针对红壤与黑土分别采用类Fenton法与Fenton法,在H2O2投加浓度为1 mol·L-1,含铁催化剂浓度为0.25 mol·L-1,土水比为1∶3,反应时间为1h的条件下,红壤及黑土中DPAA的降解率均可达到65%以上.HPLC-MS/MS的分析结果表明,DPAA可脱苯环形成降解产物苯砷酸(phenylarsinic acid,PAA),而PAA进一步氧化生成无机砷,这可能是Fenton/类Fenton法降解DPAA的途径之一.     

微孔曝气与覆盖对城市重污染河道底泥磷形态分布及释放过程的影响

采用自行研发的泥-水界面微孔曝气系统,开展了底泥表面曝气和覆盖对城市重污染河道底泥磷释放及形态分布规律的影响研究.结果表明,微孔曝气能够有效提高上覆水的溶解氧(DO)和沉积物的氧化还原电位(Eh),能够将泥-水界面Eh维持在-100 m V左右,DO提高到6 mg·L-1以上.与对照比较,原位覆盖处理的上覆水DO和Eh有一定提高,但仍明显低于微孔曝气处理.与对照相比较,微孔曝气处理均有效降低上覆水中总磷(TP)和溶解性正磷酸盐(PO3-4)的含量.试验结束时,微孔曝气(A)和微孔曝气+原位覆盖处理(A+C)上覆水中TP含量由初始的0.201 mg·L-1分别降至0.062 mg·L-1和0.050 mg·L-1;上覆水中PO3-4含量由0.086 mg·L-1和0.078 mg·L-1分别降至0.026 mg·L-1和0.023 mg·L-1.与对照相比,微孔曝气处理明显降低了底泥间隙水中TP的浓度,在整个培养期间,其TP含量平均下降38.8%(A)和47.9%(A+C).底泥原位覆盖处理对抑制泥-水界面磷释放能力要弱于微孔曝气处理,而且在试验后期(50 d),上覆水中TP和PO3-4的含量均有所反弹.不管有无覆盖,泥-水界面微孔曝气处理均显著改变了表层底泥磷形态分布特征,显著降低了底泥中铁铝结合态磷(Fe/Al-P)组分比例,而钙结合态磷(Ca-P)含量比例却出现明显增加.单一的表面覆盖处理对底泥磷形态分布特征没有显著影响(P0.05).研究表明,与单一的处理效果相比较,泥-水界面纳米微孔曝气处理,并结合底泥原位覆盖,更有利于抑制城市重污染河道泥-水界面中磷的释放风险.     

胎盘内多环芳烃分布及源解析研究

探讨多环芳烃在胎盘中的分布,并对其进行源解析。从2012年6月—2013年6月在云南省第一人民医院产科分娩的产妇中随机抽取30例,利用气相色谱-质谱联用仪(GC-MS)检测其胎盘中多环芳烃的含量;比较胎盘的中央部分和边缘部分多环芳烃含量的差异;对多环芳烃进行源解析,探讨其主要来源。胎盘中检测到多种多环芳烃成分;其中2~4个苯环的多环芳烃占总量的90%以上,尤其是萘、苊、芴、菲、蒽、芘、荧蒽的含量较高;萘、苊烯、苊、茚并(1,2,3-c,d)芘、二苯并(a,h)蒽5种多环芳烃在胎盘中央的含量高于边缘,具有显著性差异(P0.05),其他多环芳烃在胎盘中央和边缘的含量无显著性差异(P0.05)。多环芳烃源解析提示80%研究对象体内的多环芳烃主要来自石油产品的燃烧或暴露于石油产品。     

Effects of initial decomposing leaf litter of Cinnamomum camphora on the growth and physiology of Impatiens balsamina北大核心CSCD

A pot experiment was conducted to study the allelopathic effects of initial decomposing leaf litter of Cinnamomum camphora on growth and physiology of Impatiens balsamina. Three leaf litter treatments included 20, 40 and 80 g of C. camphora leaf litter mixed with 8 kg of soil, namely T1, T2, and T3, respectively. In order to test the effect of leaf litter addition on the permeability and ventilation of soil simultaneously, a parallel trial with steamed leaf litter was conducted with the three treatments of the leaf litter. The leaf litter was steamed for 2 d to remove the secondary metabolites as much as possible, dried, and then mixed with 8 kg of soil, namely Z1, Z2, and Z3, respectively. No leaf litter was added in control (CK). The growth parameters of I. balsamina were determined at the 20 d, 60 d, 100 d and 120 d after sowing and the main physiology indicators were determined at the 60 d. The results indicated that: (1) The ground surface diameter and height of I. balsamina were inhibited significantly at 60 d (P < 0.05). Photosynthetic pigments and gas exchange parameters of I. balsamina were inhibited significantly at 60 d, and the inhibition effect was stronger with increased amount of leaf litter addition. The chlorophyll content, Pn and Ls decreased significantly with increased amount of leaf litter (P < 0.05). The activity of superoxide dismutase (SOD) and peroxidase (POD) in leaves of I. balsamina decreased with the increase of leaf litter addition. The content of MDA in treatments T1, T2 and T3 were all higher than that in CK, which indicated that I. balsamina suffered oxidative damage in a certain degree. The content of free proline (Pro) and soluble sugar (SS) in leaves of I. balsamina decreased significantly with the increase of the leaf litter (P < 0.05), while the content of soluble protein (SP) increased. (2) In the parallel trial, 60 d after sowing, no obvious difference was observed between CK and any steamed leaf litter treatment in terms of the morphological and physiological features stated above (P > 0.05). It indicated that the soil physical properties were not greatly influenced by leaf litter addition in the dose interval designed, or that the release of secondary metabolites from decomposing leaf litter was probably a better reason to explain the inhibition of leaf litter treatment to I. balsamina growth. (3)The compound effect (CE) of leaf litter decomposition on I. balsamina was enhanced with increase of the leaf litter, to 0.169, 0.354, and 0.497, respectively, in treatments of T1, T2 and T3. The study indicated that initial decomposition of C. camphora leaf litter in soil reduces the content of photosynthetic pigments, inhibits photosynthetic capacity and resistance physiology of I. balsamina, weakens its adaptability to the environment, and restrains growth of the plant. © 2015, Science Press. All rights reserved.     

Increasing polybrominated diphenyl ether (PBDE) contamination in sediment cores from the inner Clyde Estuary,UK

The concentrations of 16 polybrominated diphenyl ether (PBDE) congeners in six short sediment cores from the Clyde Estuary were determined by gas-chromatography mass-spectrometry. Total PBDE concentrations ranged from 1 to 2,645 μg/kg and the average concentration was 287 μg/kg. BDE-209 was the main congener and varied from 1 to 2,337 μg/kg. Elevated total PBDE concentrations were observed close to the sediment surface in the uppermost 10 cm of four of the six sediment cores. Comparison of the down core PBDE profiles revealed that the increase was driven by the accumulation of deca-BDE. Although the deca-BDE mix was dominant, the presence of lower molecular weight congeners BDE-47, BDE-99, BDE-183 and BDE-153 at most sediment intervals suggested additional sources of penta-BDE and octa-BDE pollution. Changing PBDE source input was the major factor in influencing the proportion of nona-brominated congeners, although other explanations such as post burial photo-debromination of BDE-209 cannot be entirely discounted. A clear cascading to lower hepta-, hexa-, and penta-homologues was not found. The increase in total PBDE concentrations and particularly the deca-BDE may possibly be ascribed to the use and subsequent disposal of electrical appliances such as televisions and computers. In the Clyde sediments, the proportion of nona-brominated congeners was higher than that reported for commercial mixtures. This might be due to changing sources of PBDEs or post burial photo-debromination of BDE-209.     

Photo-polymerization of triclosan in aqueous solution induced by ultraviolet radiation

The formation of 2,8-dichlorodibenzo-p-dioxin and other harmful degradation products in the photo-degradation process of triclosan is of increasing concern. Here we worked on the identification of polymerized products at high triclosan concentration and on the mechanism of photoreaction. Five dimmers and two trimers of triclosan were detected by liquid chromatography-mass spectrum analysis. 2,8-dichlorodibenzo-p-dioxin was also identified by comparing with an authentic standard. Relatively low pH and high concentration favored the polymerization of triclosan. Three main routes of photoreaction were postulated, namely dechlorination, ring closure and polymerization.     

Preparation and assay of C-glucosyltransferase from roots of Pueraria lobata

C-glucosyltransferase (EC 2.4.1.X) is one of the key enzymes for the biosynthesis of puerarin. This paper describes the methodology in purification and assay of the enzyme for the first time in Puerarin lobata (Wild.) Ohwi. C-glucosyltransferase from roots of P. lobata was extracted and partially purified by (NH4)2SO4 saturation. The effects of pH, temperature, and substrate concentration on the activity of the enzyme were investigated. The properties of the puerarin produced by C-glucosyltransferase were studied by thin layer chromatography (TLC) and high performance liquid chromatography (HPLC). The peak activity of C-glucosyltransferase was detected in fraction of by 80% saturation of (NH4)2SO4 and the optimal conditions for enzymatic reaction were 35.5 micromol l(-1) of isoliquiritigenin and 560 micromol l(-1) of UDP-G at pH 8.1, 28 degrees C for 1 h. Mn2+ at 1 mmol l(-1) and Al3+ at 1 mmol l(-1) increased the enzyme activity, while Mg2+ inhibited its activity. The enzyme activity in Nicotiana tabacum and P. lobata were detected under the above assay conditions. Higher activity was found in roots than in leaves and stems of P. lobata, while no enzyme activity was detected in leaves of N. tabacum. It was the first time that activity of C-glucosyltransferase, which transforms isoliquiritigenin to puerarin, was detected in P. lobata.     

Bioreduction of nitrate in groundwater using a pilot-scale hydrogen-based membrane biofilm reactor

A long-term pilot-scale H₂-based membrane biofilm reactor (MBfR) was tested for removal of nitrate from actual groundwater. A key feature of this second-generation pilot MBfR is that it employed lower cost polyester hollow fibers and still achieved high loading rate. The steady-state maximum nitrate surface loading at which the effluent nitrate and nitrite concentrations were below the Maximum Contaminant Level (MCL) was at least 5.9 g·N·(m²·d)^?1, which corresponds to a maximum volumetric loading of at least 7.7 kg·N·(m³·d) ^?1. The steady-state maximum nitrate surface area loading was higher than the highest nitrate surface loading reported in the first-generation MBfRs using composite fibers (2.6 g·N·(m²·d)^?1). This work also evaluated the H₂-utilization efficiency in MBfR. The measured H₂ supply rate was only slightly higher than the stoichiometric H₂-utilization rate. Thus, H₂ utilization was controlled by diffusion and was close to 100% efficiency, as long as biofilm accumulated on the polyester-fiber surface and the fibers had no leaks.