气相色谱-质谱法分析饮用水源水中甲基汞

采用自动固相萃取-气质联用法分析饮用水源中的甲基汞,通过巯基棉小柱萃取大体积(5L)水样后,选择离子扫描方式(SIM)进行定量。实验对比国家标准方法具有更好的线性关系,实际操作简单快捷,灵敏度高。3个浓度水平进行加标回收实验,回收率分别大于71.0%、74.4%、76.0%。对10μg/L浓度重复进样6次,相对标准偏差(RSD)为4.8%。该方法检出限可达到3×10-4μg/L,满足饮用水源水中甲基汞标准限值要求。     

Chemical composition of different size ultrafine particulate matter measured by nanoparticle chemical ionization mass spectrometer

New particle formation (NPF) is the primary source of nanoparticles and contributes a large number of concentrations of cloud condensation nuclei. In recent years, field campaigns and laboratory experiments have been conducted to promote cognition of the mechanism for NPF and its following growth processes. The chemical composition measurement of nanoparticles could help deepen understanding of the initial step of particulate matter formation. In this work, we developed a nanoparticle chemical ionization mass spectrometer to measure nanoparticles' chemical compositions during their initial growth stage. Meanwhile, a non-radioactive ion source was designed for aerosol charging and chemical ionization. Time of flight mass spectrometer coupled with integrated aerosol size selection and collection module would guarantee the picogram level detection limit and high-resolution ability to measure the matrix of ambient samples. The performance of this equipment was overall evaluated, including the transmission efficiency and collection efficiency of custom-built nano differential mobility analyzer, chemical ionization efficiency, and mass resolution of the mass spectrometer. The high sensitivity measurement of ammonium sulfate and methylammonium sulfate aerosols with diameters ranging from 10 to 25 nm could guarantee the application of this instrument in the ambient measurement.     

An inverse model for the analysis of the Venice lagoon food web

A steady-state model of the Venice lagoon food web was constructed, based on a comprehensive set of data, which were collected in the years 2001-2005. Energy flows were estimated by means of an inverse methodology of constrained optimization based on the Minimum Norm criterion, i.e. on the minimization of both the sum of squares of the residuals and of the sum of squares of energy flows. The solution was constrained by a set inequalities, which were derived from general eco-physiological knowledge and site specific data on energy flows. The trophic network was represented by thirty-two nodes, including single-species compartments for the species of high economical or ecological relevance. Mass balance equations were weighted, in order to obtain meaningful results in presence of large differences, up to 5 orders of magnitude, among biomasses. A perturbation technique was applied, with the purpose of reducing the risk of finding solutions heavily affected by the set of constraints and of obtaining a more robust representation of the energy flows. The main patterns of energy flow are consistent with those obtained in previous attempts at modelling the Venice lagoon food web. Micro- and macro-phytobenthos account for the largest fraction of the primary production. Energy is then transferred towards higher trophic levels by means of two main pathways: the recycling of dead biomass through the detritus compartment and the direct consumption by grazers. The first pathway is the most important and accounts for approximately two/thirds of the energy transferred to the second trophic level.     

碱消解法测定固体废物中六价铬的研究

用碱性消解液对固体废物进行预处理,所得消解溶液用火焰原子吸收光谱法进行测定。结果表明:该方法在0.00~8.00mg/L范围内呈良好线性关系,检出限为2.00mg/kg(样品以计2.5g计)。实际样品测定的RSD为1.37%~9.35%,加标回收率为85.5%~125%。消解溶液同时用二苯碳酰二肼分光光度法进行测定,结果显示,两种方法测定的结果没有显著差异,进一步说明了采用火焰原子吸收光谱法测定固体废物中Cr6+的准确性与可靠性。     

碱消解-P&T-GC-AFS法同时测定土壤中的甲基汞和乙基汞研究

建立了碱消解-吹扫捕集-气相色谱-原子荧光光谱法(P&T-GC-AFS)同时测定土壤中甲基汞和乙基汞的分析方法.样品在90℃条件下经氢氧化钾/甲醇消解2.5 h,调节pH为5.40,并丙基化衍生后,采用P&T-GC-AFS法测定.方法对甲基汞、乙基汞的线性相关系数分别为0.999 7、0.999 6,检出限分别为0.26、0.41 ng·g -1.在不同质量浓度水平上进行加标回收率实验,甲基汞、乙基汞的回收率分别为90.5%~93.3%、86.5%~89.6%.该方法样品前处理简单、检出限低,适合批量测定土壤中甲基汞和乙基汞.     

Numerical analysis of the effects of fluctuations of discharge capacity on transient flow field in gas well relief line

Transient gas flow in relief line is computed to determine the effects of fluctuations of discharge capacity on flow field. Based on the theories of computational fluid dynamics and aerodynamics, the solution and the analysis were carried out using finite volume CFD solver FLUENT 13.0. Flow fields in seven working conditions were simulated in the numerical investigation and their results were compared. The results showed that the fluctuations of discharge capacity, including extent and period, exert obvious effects on transient gas flow field in relief line. The larger the fluctuation extent and the shorter the fluctuation period, the more significant is the effect. The application method of simulation results is provided to guide the laying and fixing of pipelines, which is verified by filed measurement.     

Numerical analysis of phase behavior during rapid decompression of rich natural gases

The effect of the condensation process on the gas and liquid phase behavior during rapid decompression of rich natural gases is studied in the paper numerically. A one-dimensional mathematical model of transient thermal two-phase flow of compressible multi-component natural gas mixture and liquid phase in a shock tube is developed. The set of mass, momentum and enthalpy conservation equations are solved for the gas and liquid phases. The approach to model a liquid condensation process during rapid decompression of rich natural gas mixture is proposed. The mass transfer between the gas and the liquid is taken into account by introducing the appropriate terms into the governing equations. Thermo-physical properties of multi-component natural gas mixture are calculated by solving the Equation of State (EOS) in the form of the Soave–Redlich–Kwong (SRK-EOS) model. The proposed liquid condensation model is integrated into the GDP model. A simple case of GDP model, where the liquid was not considered, was extensively validated on base and dry natural gases. The proposed two-phase model is validated against the experiments where the decompression wave speed was measured in rich natural gases at low temperature. It shows a good agreement with the experimental data.     

Pyrolysis behaviors of oil sludge based on TG/FTIR and PY-GC/MS

Pyrolysis is an alternative technology for oil sludge treatment. Thermogravimetric Analysis-Fourier Transform Infrared Spectroscopy and Pyrolysis-Gas Chromatography/Mass Spectrometry were employed to investigate the pyrolysis process and products of oil sludge. The pyrolysis process was divided into five stages: drying and gas desorption, oil volatilization, main pyrolysis, semi-coke charring, and mineral decomposition. The main reaction temperatures ranged from 497.6 K to 753.2 K. The products were mainly composed of pairs of alkane and alkene (carbon number ranges from 1 to 27). The mechanisms consisted of random chain scission followed by end chain scission at high temperatures with volatilization occurring during the whole process. This study is useful not only for the proper design of a pyrolysis system, but also for improving the utilization of liquid oil products.     

The impact of climate changes on mass events in China

There is an increasing number of “mass events” in mainland China. My study extends the current studies to the context of China and tries to examine the potential impacts of climate changes on human conflicts in China. The results suggest a strong linkage between the deviation of monthly mean temperature from the historical mean and the number of mass events in a province. If the current trend of warming persists, in the next 6–8 decades, the number of mass events in China will increase by over 8.8%.     

Single- and dual-porosity modelling of flow in reclaimed mine soil cores with embedded lignitic fragments

Lignitic mine soils represent a typical two-scale dual-porosity medium consisting of a technogenic mixture of overburden sediments that include lignitic components as dust and as porous fragments embedded within a mostly coarse-textured matrix. Flow and transport processes in such soils are not sufficiently understood to predict the course of soil reclamation or of mine drainage. The objective of this contribution is to identify the most appropriate conceptual model for describing small-scale heterogeneity effects on flow on the basis of the physical structure of the system. Multistep flow experiments on soil cores are analyzed using either mobile–immobile or mobile–mobile type 1D dual-porosity models, and a 3D numerical model that considers a local-scale distribution of fragments. Simulations are compared with time series' of upward infiltration and matric potential heads measured at two depths using miniature tensiometers. The 3D and the 1D dual-permeability models yielded comparable results as long as pressure heads are in local equilibrium; however, could describe either the upward infiltration or the matric potential curves but not both at the same time. The mobile–immobile type dual-porosity model failed to describe the data. A simultaneous match with pressure heads and upward infiltration data could only be obtained with the 1D dual-permeability model (i.e., mobile–mobile) by assuming an additional restriction of the inter-domain water transfer. These results indicate that for unsaturated flow conditions at higher matric potential heads (i.e., here >− 40 hPa), water in a restricted part of the fragment domain must be more mobile as compared to water in the sandy matrix domain. Closer inspections of the pore system and first neutron radiographic imaging support the hypothesis that a more continuous pore region exists at these pressure heads in the vicinity of the lignitic fragments possibly formed by fragment contacts and a lignitic dust interface-region between the two domains. The results suggest that the small-scale structure is too complex as to be represented by weighted contributions of individual components alone.