High resolution proton NMR spectroscopy of human amniotic fluid

Human amniotic fluid (HAF) is a dynamic system whose characteristics depend on continuous interchanges between fetal and maternal circulations. HAF reflects not only the environment of the fetus but may also provide information about fetal development or pathology. The concentration of HAF constituents varies with gestational age and pathological states. The number of the compounds currently implicated in fetal developmental pathology are relatively few. Currently used assay methods are not adequate to totally explain or predict the complex biochemistry of the fetus. The purpose of this work was to investigate HAF with NMR spectroscopy. In the present study HAF was obtained from 47 women undergoing routine amniocentesis. Cells were separated for karyological analysis and the supernatant was acid-extracted, lyophilized and re-suspended in D₂0 resulting in a concentration increase over native fluid. ¹H NMR spectra were obtained at 360 MHz and 60 MHz. Eighteen compounds including several amino acids, were identified using parallel reference and standard addition protocols. NMR spectroscopy detected compounds of known clinical importance including glucose, leucine, isoleucine, lactate and creatinine. In conclusion, we have demonstrated that a number of physiologically relevant compounds are readily observable in HAF using ¹H NMR spectroscopy. This technique can currently provide valuable information regarding HAF composition and has the potential of being used in vivo in the future.     

染料探针技术对二级出水中优势污染物的定量检测

分别以刚果红和中性红为染料探针,建立了牛血清蛋白质(BSA)和海藻酸多糖(SA)含量与共振光散射(RLS)发射光谱强度间的线性关系;以甲苯胺蓝为染料探针,建立了腐殖酸(HA)含量与紫外吸光度间的线性关系;优化了3种标准物质的检测浓度范围及溶液p H值条件;考察了染料探针分析方法对标准物的二元和三元混合样品中的回收率.结果表明在适宜的浓度范围内,BSA、HA、SA浓度与染料探针光谱强度间的线性相关系数R0.98,3种标准物在混合样品中的回收率不小于95%,标准误差低于0.11%.以紫外光谱和3D-EEM光谱特征作为城市污水二级出水样品中蛋白质、多糖和腐殖酸的定性依据,确认了4种二级出水样品中的优势污染物.通过染料-探针技术与国标法测得的多糖和蛋白质质量浓度的相对偏差在1.2%~0.04%之间.     

Source profiles of particulate organic matters emitted from cereal straw burnings

Cereal straw is one of the most abundant biomass burned in China but its contribution to fine particulates is not adequately understood. In this study, three main kinds of cereal straws were collected from five grain producing areas in China. Fine particulate matters （PMzs） from the cereal straws subjected to control burnings, both under smoldering and flaming status, were sampled by using a custom made dilution chamber and sampling system in the laboratory. Element carbon （EC） and organic carbon （OC） was analyzed. 141 compounds of organic matters were measured by gas chromatography-mass spectrum （GC-MS）. Source profiles of particulate organic matters emitted from cereal straw burnings were obtained. The results indicated that organic matters contribute a large fraction in fine particulate matters. Levoglucosan had the highest contributions with averagely 4.5% in mass of fine particulates and can be considered as the tracer of biomass burnings. Methyloxylated phenols from lignin degradation also had high concentrations in PM2.5, and contained approximately equal amounts of guaiacyl and syringyl compounds. 13-Sitostrol also made up relatively a large fraction of PMz5 compared with the other sterols （0.18%-0.63% of the total fine particle mass）. Normal alkanes, PAHs, fatty acids, as well as normal alkanols had relatively lower concentrations compared with the compounds mentioned above. Carbon preference index （CPI） of normal alkanes and alkanoic acids showed characteristics of biogenic fuel burnings. Burning status significantly influenced the formations of EC and PAHs. The differences between the emission profiles of straw and wood combustions were displayed by the fingerprint compounds, which may be used to identify the contributions between wood and straw burnings in source apportionment researches.     

碱处理对互花米草理化特性的影响研究

研究了5%的NaOH溶液固态处理互花米草后,互花米草的物质结构、物质组成以及水浸提液理化特性的变化.结果表明,经5%的NaOH溶液处理48h后,互花米草的木质纤维结构受到破坏,木质素大分子被碎片化,一些含氮的有机物和碳水化合物受到破坏,导致互花米草水浸提液的COD、TN和有机氮含量大幅增加,分别增加了333.90%、45.26%和25.83倍.对纤维素含量和纤维素结晶度的影响不大,但纤维素的结晶区可能发生了一定的重结晶.半纤维素受到较大程度的破坏,半纤维素含量大幅降低了27.65%,产生了一些羧基类物质.碱处理后,木质素的包裹作用被去除,互花米草的生物降解性能提高.     

Scanning proton microprobe microanalysis for the assessment of homogeneity of IAEA urban dust reference materials

In order to develop new reference materials for microanalytical nuclear techniques, scanning proton microprobe(SPM) technique was used to determine homogeneity level within 100x200 μm2 micro-area on the small pieces of IAEA urban dust reference materials. The experimental methods were described in detail. The results show that IAEA-396A/M Vienna urban dust is homogeneous enough for small sample analysis of standard reference material (SRM).     

基于EEM-PARAFAC解析厌氧生物滤池对城市污染河流中DOM的转化特性

为探究厌氧生物滤池(AF)处理城市污染河流的最佳工况和运行效能,以新河河水为研究对象,运用三维荧光光谱结合平行因子法(EEM-PARAFAC),研究AF中试试验系统在不同水力停留时间(HRT)及温度条件下对溶解性有机物(DOM)的转化特性. 结果表明:①河水中DOM主要包含3种荧光组分,其中,C1为类腐殖质物质,C2为类蛋白物质,C3为类腐殖质物质,类蛋白和类腐殖质物质平均占比分别为53.45%和46.55%. ②AF运行稳定后COD平均去除率为30.75%,出水UV₂₅₄降低19.80%;荧光组分分析表明,DOM的降低主要归因于C2和C3的有效转化,且提高温度和HRT有助于DOM的进一步降低. ③UV₂₅₄和<10 kDa的DOM沿程逐步减小,3~10 kDa和<3 kDa的DOM去除率分别为64.29%和22.81%;沿程出水三维荧光光谱显示,AF前端微生物活性较高,C1和C3变化较小,C2先升高后逐步下降,最终出水DOM总荧光强度出现明显的降低,表明AF第1级滤层是DOM去除和转化的主要区域. 研究显示,常温且HRT=24 h工况下,AF能够在一定程度上将难降解有机物转化为易降解有机物,有效去除城市污染河流中的DOM,可作为处理城市污染河流的潜在预处理手段.      

Characteristics of isothermal adsorption and desorption of aluminum ion to/from humic acids

The adsorption and desorption characteristics of Al3+ to/from humic acids at di erent pH, ionic strength, and temperature were studied by the C-25 glucosan-gel chromatography method. The results showed that the maximum adsorption amount (Qmax) and adsorption constant (k) increased, whereas, the absolute value of standard thermodynamic molar free energy change ( G0 m) decreased with the increase of pH at constant ionic strength and temperature. With ionic strength increasing from 0 to 0.15 mol/L, Qmax and k increased and the absolute value of G0 m decreased at constant pH and temperature. High temperature was unfavorable for the adsorption reaction, as indicated by the dramatic decrease of Qmax and the absolute value of G0 m with an increase in temperature. The standard thermodynamic molar free energy change ( G0 m) and the standard thermodynamic enthalpy change ( H0m ) of the adsorption reaction were both negative, suggesting that adsorption reaction was spontaneous and exothermic. The desorption rate of HA-Al3+ complex accelerated with the decrease of pH, and a significant linear relationship could be obtained between pH and the desorption rates of Al3+ from humic acids. These results demonstrated that the Al3+ adsorption reaction was a “biphase” reaction, and adsorption occurred at both the interior and exterior adsorption sites of humic acids.     

北京市大气气溶胶PM2.5中水溶性有机酸的测定

采用毛细管电泳的方法对北京大气PM_2.5中低分子量二元羧酸、醛酸、酮酸和甲磺酸等10种水溶性有机酸进行了测定.方法的定量检测限为110～280 μg/L(提取液),峰面积的相对标准偏差为1.7%～6.0%,标准工作曲线的线性相关系数为0.995～0.999.北京夏、秋、冬3季10种有机酸的总量平均分别为721ng/m³、362ng/m³、325 ng/m³,浓度水平总体上与国外大城市相当.其中乙二酸的含量最为丰富.通过各种有机酸浓度的季节变化规律,简要地探讨了它们的来源特征.     

我国土壤和沉积物中富里酸标准样品的提取和表征

参照国际腐殖酸协会(IHSS)推荐的方法,从北京鹫峰森林土壤和太湖竺山湖区表层沉积物中分别提取FA(富里酸)样品.采用元素分析、紫外-可见光谱、三维荧光光谱、傅里叶红外光谱以及13C NMR分析对FA样品进行了表征,并与IHSS FA进行比较.结果表明:土壤FA和沉积物FA与IHSS FA在元素组成、灰分含量及结构上基本相似,与IHSS FA具有一定的可比性,可以作为我国FA的标准样品.由于FA的来源及其形成环境的不同,各FA之间在组成和结构上存在一定的差异.IHSS FA和沉积物FA的芳香性均略高于土壤FA,这可能是由于水环境系统中含有大量的水生植物以及微生物降解作用所致.3种FA的极性排序为土壤FA>沉积物FA> IHSS FA.      

Nano-TiO2回收过程中SO42-对不同混凝剂混凝过程的影响

为了降低纳米TiO₂使用成本,采用不同混凝剂对纳米TiO₂悬浊液进行固液分离.通过考察浊度去除率、出水pH值的变化情况,并结合X射线光电子能谱（XPS）、傅里叶红外光谱（FTIR）、固体核磁（NMR）、扫描电镜（SEM）及能谱分析（EDS）表征,探究了纳米TiO₂回收过程中SO₄^2-对不同混凝剂混凝过程的影响.结果表明,当使用AlCl₃作混凝剂时（0.1mmol/L）,SO₄^2-浓度从0.0mmol/L增加到20.0mmol/L,浊度去除率降低了0.80%,絮体粒径从450μm下降到215 μm,而强度因子无明显变化.低聚合态的Al_a不与SO₄^2-结合,混凝过程中通过吸附架桥和网捕卷扫的作用形成大量无定形的Al （OH）₃.当使用Al₁₃作混凝剂时,再生长后絮体的粒径随着SO₄^2-浓度的增加而下降,S-O峰的红移证明有新的含S聚合物产生,Al 2p的峰均向较高的结合能移动证明生成的絮体不是Al （OH）₃.     

强化生物除磷过程中污泥胞内糖原的红外光谱分析

采用傅里叶中红外光谱对强化生物除磷过程中污泥胞内糖原物质进行了表征,并将污泥样品与糖原标样的红外光谱进行对比,确认糖原物质在1020 cm-1峰附近有较明显的特征吸收贡献.因此,采用红外光谱945~1150 cm-1区域内的吸收光谱数据,结合测得胞内糖原的含量,应用偏最小二乘法和BP神经网络算法分别建立了污泥红外光谱与糖原含量的定量分析模型.结果显示,偏最小二乘法得到的测量值与预测值具有较小的平均绝对误差(MAE),其相关系数达到0.921.     

微生物絮凝剂ZS-7的纯化及其结构特征研究

采用透析、乙醇沉淀、凝胶过滤层析对微生物絮凝剂ZS-7进行了纯化.经鉴定纯化后的微生物絮凝剂ZS-7是一种新型的糖蛋白,其产量大约为0.98 g/L发酵液.ZS-7主要由多糖和蛋白质组成,含量分别为91.5%和8.4%.进一步的分析表明ZS-7中含有酸性多糖包括糖醛酸(16.4%)、丙酮酸(7.1%)和乙酸(0.5%).采用凝胶色谱法测得ZS-7的相对分子质量为6.89×104.红外光谱、X射线能谱图和核磁共振图谱说明糖蛋白絮凝剂ZS-7含有羟基、氨基、羧基、甲氧基和磺酸等功能性基团.单糖组成分析说明ZS-7主要由鼠李糖、甘露糖、葡萄糖和半乳糖组成,各单糖的摩尔比大致为:半乳糖∶葡萄糖∶甘露糖∶鼠李糖=142∶2.2∶4.5∶3.4.     

不同源胡敏酸的表征及其对磺胺嘧啶光降解的影响

以国际腐殖酸协会(IHSS)推荐的方法为基础,对四川省绵阳市青义镇泥炭地、水稻田及凋落物覆盖土层中的胡敏酸(HA)进行提取纯化.通过元素组成、紫外-可见光谱、傅里叶红外光谱及三维荧光光谱对各HA样品的结构特性进行对比分析,并探讨各HA对磺胺嘧啶光降解行为的影响.结果表明:泥炭地HA(NTHA)、水稻田HA(SDHA)、凋落物覆盖土HA(LYHA)及市售商品HA(SPHA)均主要由C、H、O、N 4种元素构成,芳香性大小为SPHANTHALYHASDHA;与提取的HA相比,SPHA含有更多的含氮类、芳香类、脂类化合物及含氧官能团,腐殖化程度高,可能含有较多的光活性基团;磺胺嘧啶(SDZ)在黑暗条件下表现出良好的稳定性,而紫外光照条件下发生了缓慢降解,光降解过程符合一级反应动力学;添加不同来源HA后,各体系SDZ的光降解速率均大于纯水溶液,且HA表现出的促进作用大小为SPHASDHANTHALYHA,这可能与各HA的腐殖化程度相关.     

Bioaccumulation characterization of uranium by a novel Streptomyces sporoverrucosus dwc-3

The biosorption mechanisms of uranium on an aerobic bacterial strain Streptomyces sporoverrucosus dwc-3, isolated from a potential disposal site for (ultra-)low uraniferous radioactive waste in Southwest China, were evaluated by using transmission electron microscopy (TEM), energy dispersive X-ray (EDX) analysis, Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), proton induced X-ray emission (PIXE) and enhanced proton backscattering spectrometry (EPBS). Approximately 60% of total uranium at an initial concentration of 10 mg/L uranium nitrate solution could be absorbed on 100 mg S. sporoverrucosus dwc-3 with an adsorption capacity of more than 3.0 mg/g (wet weight) after 12 hr at room temperature at pH 3.0. The dynamic biosorption process of S. sporoverrucosus dwc-3 for uranyl ions was well described by a pseudo second-order model. S. sporoverrucosus dwc-3 could accumulate uranium on cell walls and within the cell, as revealed by SEM and TEM analysis as well as EDX spectra. XPS and FT-IR analysis further suggested that the absorbed uranium was bound to amino, phosphate and carboxyl groups of the cells. Additionally, PIXE and EPBS results confirmed that ion exchange also contributed to the adsorption process of uranium.     

Distribution and sources of solvent extractable organic compounds in PM2:5 during 2007 Chinese Spring Festival in Beijing

The solvent extractable organic compounds (SEOC), including n-alkanes, polycylic aromatic hydrocarbons, fatty acids, anddicarboxylic acids in PM2.5 during the 2007 Chinese Spring Festival in Beijing, were measured via gas chromatography-massspectrometry for determining the characteristics and sources of these organic pollutants. The concentrations of total n-alkanes, PAHs,and organic acids before Chinese Spring Festival Eve (1025.5, 95.9, and 543.3 ng/m3, respectively) were higher than those after (536.6,58...     

Molecular structures and associations of humic substances in the terrestrial environment

Here we show, for the first time, evidence of the primary molecular structures in humic substances (HS), the most abundant naturally occurring organic molecules on Earth, and their associations as mixtures in terrestrial systems. Multi-dimensional nuclear magnetic resonance (NMR) experiments show us that the major molecular structural components in the mixtures operationally defined as HS are aliphatic acids, ethers, esters and alcohols; aromatic lignin derived fragments; polysaccharides and polypeptides. By means of diffusion ordered spectroscopy, distinct diffusion coefficients consistent with relatively low molecular weight molecules were observed for all the components in the mixtures, and saccharides were the largest single class of component present. Liquid chromatography NMR confirmed that HS components can be easily separated and nuclear Overhauser effect (NOE) enhancements support the finding that the components are of relatively low molecular weight <~2,000 Da. The widely recognized properties of HS, i.e., characteristics indicative of crosslinked, macromolecular networks, can now be explained as aggregation of mixtures, most likely instigated by complexation with metal cations.     

SGO/PVDF-g-PSSA复合质子交换膜的制备及抗污染性研究

为更好的提高PVDF-g-PSSA质子交换膜的性能,将磺化氧化石墨烯（SGO）与PVDF-g-PSSA共聚物混合制得SGO/PVDF-g-PSSA复合质子交换膜.用傅里叶变换红外光谱（FTIR）、X射线光电子能谱（XPS）以及X射线测定仪（XRD）证实了GO的成功磺化.对复合膜进行SEM表征并考察了复合膜的主要性能,得到了最佳SGO掺加量.使用耗散型石英晶体微天平（QCM-D）研究了复合膜的抗污染性能.实验结果表明：当SGO添加量为1.0%时,复合膜的含水率达到44.34%,质子传导率为0.085S/cm,综合性能达到最佳.QCM-D实验表明,在纯水和50mmol/L PBS条件下,复合膜表面的BSA吸附量均最低,且|ΔD/ΔF|最大,说明吸附层较为疏松,复合膜具有较好的抗污染性.     

DC反应器处理中药废水过程中出水的光谱分析

采用三维荧光(EEM)与傅立叶红外(FTIR)光谱技术,对不同运行条件下,新型双循环(DC)厌氧反应器处理中药废水的出水情况进行了分析,以期为厌氧反应器的有效监控提供新思路.结果表明,在HRT为24h时,COD去除率为94%左右,平均产气率达到0.37m3CH4/kgCOD,出水的EEM光谱中,Ex/Em=420/470nm处出现了明显的辅酶F420吸收峰;而HRT减少为12h后,虽然COD去除率仍达到90%左右,但出水EEM光谱中,辅酶F420的吸收峰有所降低,并出现了类富里酸的吸收峰,表明不宜再继续减少HRT.当温度由30oC降低为20oC时,温度的变化影响了厌氧污泥的性状,使得出水的FTIR光谱中3400cm-1处的吸收峰由原来的钝峰变为尖峰.而在进水中添加大黄酸后,造成了反应器内有机酸的累积,产甲烷菌活性受到严重影响,出水的EEM光谱中,腐殖酸与类富里酸的吸收峰显著增强.     

利玛原甲藻中大田软海绵酸和鳍藻毒素-1提取与纯化

批量培养产生腹泻性贝类毒素的利玛原甲藻,甲醇提取超声破碎后的藻细胞;用大孔吸附树脂HP20富集其胞外毒素并进行毒素的初步纯化。经制备型高效液相色谱法分离,分别得到毫克级的大田软海绵酸和鳍藻毒素-1固体。经核磁共振氢谱和高分辨质谱确认结构,定量核磁确定纯度,得到的大田软海绵酸和鳍藻毒素-1纯度分别为99.39%和99.26%,满足标准物质制备要求。     

AF+BAF用于处理树脂化工集中区废水厂尾水的研究

采用厌氧滤池(AF)+曝气生物滤池(BAF)工艺处理树脂化工废水,曝气生物滤池以陶粒为生物载体,进水COD为200~300 mg·L-1,实验规模均为2~4 L·d-1.实验表明,采用AF+BAF工艺对化工园区尾水有较好的处理效果,在AF停留24h,BAF停留12 h的条件下,COD的去除率最高可达73.4%,NH+4-N的去除率达到93.8%.通过气相色谱-有机质谱联用仪(GC-MS)和三维荧光光谱分析发现,系统对小分子有机物和微生物代谢产物的去除显著,但对饱和烷烃和含氮杂环类物质去除效果不佳.变性梯度凝胶电泳(DGGE)谱图显示,AF中的微生物种类比原废水厂上流式厌氧池(UASB)中更为丰富,表明化工园区废水采用二次厌氧效果明显.