密度泛函理论研究碳链长度对氯化三烷基铵萃取氯化汞的影响

运用密度泛函理论方法研究了烷基碳链长度对氯化三烷基铵络合氯化汞的影响,计算结果表明,氯化三烷基铵与氯化汞的络合作用随着氯化三烷基铵中烷基碳链的增长而增强.通过对络合物的键长、Mayer键级和Mulliken电荷分析可知,电子富集在氯化三烷基铵的Cl原子上,并和Hg原子之间形成静电吸引作用.当烷基长度小于3时,烷基的电子效应影响较为明显,增强了原子之间的电子转移,使得络合物更稳定;当氯化三烷基铵烷基碳链长度大于3后,烷基链长对络合物中的电子转移不再有影响,络合物的稳定性受到烷基的几何效应影响更为明显.     

A microcalorimetric study of the action of mercuric chloride on the metabolism of mitochondria isolated from Cyprinus carpio liver tissue

After the occurrence of 'Minamata disease' in 1950, mercury aroused much more attention, and lots of studies concerned have been made. The purpose of the present paper is to study the effect of mercuric chloride on the mitochondria suspension isolated from the liver tissue of Cyprinus carpio from the direct viewpoint of energy by using the microcalorimetric method. The metabolic thermogenic curves of the mitochondria suspension at 25°C were obtained, and the mitochondria metabolic thermokinetic equations were established, from which we obtained the thermodynamic and thermokinetic parameters: thermogenic rate constant (k), heat output (Q), average heat power (P_av), etc. Experimental results indicated that low concentration of mercuric chloride (5 nmol Hg²⁺/(mg protein)) stimulates the thermogenesis of mitochondria, suggesting a strong effect of uncoupling action, while high concentration of mercuric chloride (20 nmol Hg²⁺/(mg protein)) inhibits the metabolism of mitochondria completely, suggesting a fatal effect on the phosphorylation system. The effect of Hg²⁺ on mitochondria is concentration-depended, from which the probable reaction mechanism of Hg²⁺ to the mitochondria was proposed. So the microcalorimetric method can be used in the toxicology research.     

Annular diffusion denuder for simultaneous removal of gaseous organic compounds and air oxidants during sampling of carbonaceous aerosols

A specially designed annular diffusion denuder for simultaneous removal of organic gaseous compounds and atmospheric oxidants in carbonaceous aerosol sampling is presented. Various kinds of denuder coatings were compared with respect to the collection efficiency of both organic gaseous compounds and NO₂ and ozone. The optimum sorbent is a mixture of activated charcoal and sulfite on molecular sieve. To ensure high collection efficiency over long-term field operation, two annular diffusion denuders are combined in series. The first half of the first denuder is filled with Na₂SO₃ on molecular sieve (23 cm long layer) while the second half of the first denuder and the whole second denuder are filled with activated charcoal (the total length of the charcoal section is 67 cm).     

Speciation of Mercury in two Dimictic Lakes of North-East Germany During a Period of 600 Days

Abstract

The speciation of mercury was studied with respect to (a) dissolved atomic mercury, (b) dissolved ionic mercury, and (c) total mercury in two dimictic lakes of North-East Germany. Differential pulse anodic stripping voltammetry was used for the analyses. The results show that biological processes dominate the speciation. They are responsible for high concentrations of atomic mercury and also organomercury compounds. The oxidation of atomic mercury under environmental conditions in lake water is very slow, so that the equilibrium between Hg_aq° and Hg_aq and Hg_aq ²⁺ can only be established during long periods of decreased bioactivity, as in wintertime. The sedimentation of the detritus during summer leads to a very pronounced decrease of the overall mercury in the entire water body of the lakes.     

Speciation of volatile mercury species present in digester and deposit gases

Volatile mercury compounds have been speciated in gases evolved from fermentation of sewage sludge as well as municipal waste. The species were trapped by sequential sampling, using a noble‐metal trap in series with an activated‐carbon trap. Thermally desorbed Hg⁰ and (CH₃)₂Hg were separated by GC at 70 °C and detected by cold vapour atomic fluorescence spectroscopy after thermal reduction. The amounts of mercury detected in the sewage gas correspond to concentrations in the range 50–110 ng m⁻³ for both species whereas the deposit gases were found to contain only elemental mercury. Monomethylmercury species could not be positively identified in any of the gas samples. Copyright © 1999 John Wiley & Sons, Ltd.     

α‐Cyclodextrin and methylmercury chloride: a new strategy to recover organomercurials

Methylmercury (MeHg) is one of the most toxic forms of mercury in the environment. It can be accumulated in fish through the food chain; after, consumption the fish is then dangerous to fetuses and younger children, causing abnormal brain development and nervous system disorders. Cyclodextrins (CDs) are cyclic oligosaccharides consisting of six, seven or eight units of glucose. In accord with the dimensions and hydrophilic–lipophilic properties, one can obtain inclusion of hydrophobic guests in a CD cavity. In the present work we used this characteristic of CD to obtain an inclusion compound between MeHgCl and the α‐cyclodextrin, looking for a new method to reduce MeHgCl toxicity and pre‐concentration. The inclusion compound was characterized through IR, ¹H, ¹³C NMR and Raman spectroscopy. ­X‐ray diffraction and thermal analysis (TG, DTG and DSC) methods were also used. Finally, biological tests were carried out and the minimum inhibitory concentrations (MICs) for MeHgCl, α‐cyclodextrin, the MeHgCl–CD complex and a physical mixture were determined. This host–guest strategy using cyclodextrins offers an alternative and powerful method for mercury remediation. Copyright © 2000 John Wiley & Sons, Ltd.     

氯化胆碱/尿素和氯化胆碱/甘油的性质与应用

作为绿色溶剂,离子液体在化学和物理学科引起广泛关注.低共融溶剂,如氯化胆碱/尿素和氯化胆碱/甘油,不仅被认为是一类新型的离子液体,还具有价格低廉、环境友好及合成简便等优势.为了促进氯化胆碱/尿素和氯化胆碱/甘油这两种低共融溶剂的应用,本文考察了氯化胆碱/尿素和氯化胆碱/甘油的微观结构、物理化学性质及水分对其物性的影响,并将其与传统离子液体进行了比较.此外,还分析了氯化胆碱/尿素和氯化胆碱/甘油在摩擦学及CO2分离中的潜在应用.已有研究结果表明,氯化胆碱/尿素和氯化胆碱/甘油有希望应用于摩擦学及CO2分离中,但是在大规模工业应用之前依然存在很多不确定性和瓶颈,还需要进一步在其纳米结构、实验测定及模型等方面进行研究.     

The magic of integration:Exploring the construction of dithienylethene-based infinite coordination polymers and their synergistic effect for gaseous ammonia probe applications

Infinite coordination polymers are recognized as excellent platform for functionalization.Dithienylethene motifs,which are one of the most attractive functional moieties,were incorporated into an infinite coordination polymer,to deliver a‘‘smart’’porous material that can response to external stimuli.The obtained dithienylethene-based infinite coordination polymers(named Cu-DTEDBA)share the advantages of both infinite coordination polymers(porosity and stability)and dithienylethene motifs(photochromism).The physical and chemical properties of Cu-DTEDBA were characterized by FTIR,TEM,SEM,XRD,TGA,UV–vis,EDX and BET.Moreover,the combination of dithienylethene and infinite coordination polymers gives rise to a synergistic effect,which induces functional behaviors of ammonia sensor applications.Both open and closed forms of Cu-DTEDBA exhibit distinct colorimetric change upon exposure to gaseous ammonia,which is not observed in dithienylethene free molecules.     

Direct determination of trace amounts of acetic acid using a novel ambient glow discharge ion source

<正>A novel ambient glow discharge ion source with improved line-cylinder electrodes is put forward and designed in this paper.The diameters of inner and outer electrodes are 0.16 and 4 mm respectively.With a special assembly method,a perfect coaxiality of the two electrodes is obtained.From the gas discharge experiment,it can be seen that the discharge can stably work in normal glow discharge mode.The operating currents of the ion source are in an order of milliamperes and can generate a much larger number and wider variety of reagent ions.The MS experiment shows that the ion source has higher detection sensitivity.     

Development and complete validation of a method for the determination of dimethyl mercury in air and other media

The rigorous validation of a previously developed research method for the determination of dimethyl mercury ((CH₃)₂Hg) in environmental samples is presented. During atmospheric analysis, (CH₃)₂Hg was trapped on Carbotrap™ and analyzed by thermal desorption, isothermal GC separation, and cold vapor atomic fluorescence spectrometry (CVAFS). Water samples were analyzed after direct purging of 100 mL aliquots onto Carbotrap™, while sediment and tissue samples were digested with 10 mL of 25% KOH in methanol at 60 °C and diluted to 40 mL with methanol. An ambient air-spiking manifold, which allowed simultaneous replicate sampling, was constructed in a room controlled for temperature and humidity. (CH₃)₂Hg was introduced into the feed airflow (0.4 m³ min⁻¹) from a well-calibrated diffusion cell, to obtain a concentration of approximately 5.5 ng m⁻³ as Hg. Samples were collected onto Carbotrap™ columns, and the total volumes quantified by integrating mass flow meters. Trapping efficiency was investigated over a range of sampler flow rates (0.05-0.25 L min⁻¹), volumes (2-200 L), collection temperatures (15-42 °C) and relative humidity levels (10-70%). Method detection limits (MDLs), analytical precision and accuracy were quantified for all media. Carbotrap™ was found to be the best choice as a sampling media, whereas Tenax™ was found to be inadequate due to high breakthrough (>70%). This study verified that the method is sufficiently precise, accurate and robust for field sampling at mercury contaminated sites. No interferences were observed from elevated levels of potential co-contaminants, Hg⁰ (125 ng m⁻³) and H₂S (1.27 ppmv).     

Zinc mediated reductive dimerization and cyclization of α,β-unsaturated ketones in the presence of a catalytic amount of mercury(II) chloride

The zinc mediated reductive dimerization and cyclization of α,β-unsaturated ketones gives functionalized cyclopentanols in good yield in the presence of a catalytic amount of mercury(II) chloride in N,N-dimethylformamide as solvent at room temperature. The reaction is regio- and stereo-selective producing 3,4-trans-diarylcyclopentanols selectively.     

垃圾焚烧中氯化物对重金属Pb迁移转化特性的影响

采用管式炉和模拟垃圾对垃圾中氯化物对重金属Pb迁移转化特性的影响进行了研究,使用ICP-AES(美国EPA消解方法)、SEM、EDS和XRD等对重金属浓度、灰渣表面形貌、成分和灰渣X射线衍射物相等进行了分析。结果表明,氯化物含量的增加使得Pb生成更多易挥发性物质,从而向飞灰迁移分布,但有机氯PVC的影响比无机氯NaCl的大。无机氯NaCl和有机氯PVC对焚烧中Pb迁移转化作用机理不同,NaCl易与Pb反应生成PbCl2,而PVC与Pb反应除了生成PbCl2外,还生成了Pb(ClO4)2、PbCl2O4和PbO2。同时焚烧温度和停留时间也是焚烧中Pb迁移分布的两个主要影响因素。     

Comparison of constant-current stripping chronopotentiometry and anodic stripping voltammetry in metal speciation studies using mercury drop and film electrodes

Capabilities for heavy metal speciation of anodic stripping voltammetry (ASV) and constant-current stripping chronopotentiometry (SCP) in both mercury drop (HMDE) and mercury film rotating disk (MFE-RDE) electrodes are compared. For this purpose, the Cd(II)–glycine and Cd(II)–polymethacrylate (PMA) systems are used as models of simple labile and macromolecular labile complexes adsorbing onto the electrode, respectively. The results suggest that SCP could be a valuable alternative to the more widespread ASV in this kind of study. Concerning the electrode, the MFE-RDE is less user-friendly than the HMDE, but presents a better definition of both the hydrodynamic conditions during the deposition step and the stripping regime during the oxidation. An important interference in SCP is the dissolved oxygen, which can be minimised by combining relatively large oxidation currents and low stirring rates. Moreover, for Cd–PMA, double peaks have been observed in both ASV and SCP, which seems to be due to the lack of enough ligand excess to complex the metal ions released by the amalgam oxidation. Anyway, this problem can be minimised by optimising the rotation rate of the electrode and ensuring enough ligand excess.     

Approach for rapid extraction and speciation of mercury using a microtip ultrasonic probe followed by LC-ICP-MS

A fast method for mercury extraction from biological samples based on the use of HCl leaching plus different enzymatic hydrolysis (with and without mercury complexing agents), and the use of focussed ultrasounds (2-mm microtip) is here proposed. Total mercury content in several biological samples was determined by FI-ICP-MS using a carrier solution consisting of 0.1% (v/v) HCl, 0.1% (v/v) 2-mercaptoethanol, to avoid memory effect, and 0.15% (w/v) KCl. For mercury speciation a RP18 chromatographic column coupled to ICP-MS was used. A mobile phase consisting of 0.1% (v/v) formic acid, 0.1% (v/v) HFBA, 2% (v/v) methanol, and 0.02% (w/v) mM l-cysteine at pH 2.1 was used for chromatographic separation of the mercury species in the sample extracts. Extraction procedures were validated by using 50 mg of tuna fish tissue CRM-463 (2.85 ± 0.16 mg kg⁻¹ for methylmercury). The recoveries obtained were 99 ± 3% and 93 ± 1% after acid leaching (HCl 7 M) and enzymatic extraction (15 mg protease type XIV in 2.5% (v/v) 2-mercaptoethanol), respectively. The optimal sonication conditions (5 min of exposure time and 40% of ultrasound amplitude) were applied to 5 mg of CRM-463 (88 ± 5%), 5 mg of mussel tissue (81 ± 11%) and to 2 mg of zebra fish embryos (90 ± 10%) obtaining good recoveries in all cases. Methylmecury was found to be the most abundant Hg specie in all samples. The developed method is simple and rapid (5 min sample treatment); it is suitable for very small samples and does not alter the original form of the mercury species. Thus, it is of special interest in those cases in which validation of the results may often be hampered by lack of sample availability.     

Density,viscosity, conductance,and transference number of concentrated aqueous magnesium chloride at 25°C

The density, viscosity, conductance, and transference number of aqueous magnesium chloride at 298.15°K are reported for the concentration range 0 to 5.7m. The transference numbers were determined using the emf method. It was found that the viscosity, conductance, and transference number of aqueous magnesium chloride are similar to those for aqueous nickel chloride. It was therefore tentatively concluded that incomplete dissociation and complex formation was unlikely to be of importance in nickel chloride solutions.     

Characterization of a distributed plasma ionization source (DPIS) for ion mobility spectrometry and mass spectrometry

A recently developed atmospheric pressure ionization source, a distributed plasma ionization source (DPIS), was characterized and compared to commonly used atmospheric pressure ionization sources with both mass spectrometry (MS) and ion mobility spectrometry (IMS). The source consisted of two electrodes of different sizes separated by a thin dielectric. Application of a high RF voltage across the electrodes generated plasma in air yielding both positive and negative ions. These reactant ions subsequently ionized the analyte vapors. The reactant ions generated were similar to those created in a conventional point-to-plane corona discharge ion source. The positive reactant ions generated by the source were mass identified as being solvated protons of general formula (H₂O)_nH⁺ with (H₂O)₂H⁺ as the most abundant reactant ion. The negative reactant ions produced were mass identified primarily as CO₃⁻, NO₃⁻, NO₂⁻, O₃⁻ and O₂⁻ of various relative intensities. The predominant ion and relative ion ratios varied depending upon source construction and supporting gas flow rates. A few compounds including drugs, explosives and amines were selected to evaluate the new ionization source. The source was operated continuously for 3 months and although surface deterioration was observed visually, the source continued to produce ions at a rate similar that of the initial conditions.     

Determination of mercury in polluted soils surrounding a chlor-alkali plant: Direct speciation by X-ray absorption spectroscopy techniques and preliminary geochemical characterisation of the area

Soil samples collected in the surroundings of a chlor-alkali plant in the Netherlands were characterised by synchrotron-based techniques and conventional analytical procedures, in order to evaluate the environmental impact of Hg emissions and other heavy metals present in these locations. Analysis of total metal content by inductively coupled plasma-optical spectroscopy (ICP-OES) revealed a heterogeneous contamination of Hg, with concentrations ranging from 4.3 to 1150 μg g⁻¹. In addition, significant concentrations of Cu, Ni, Pb, Zn, Mn and principally Fe were also identified within the studied samples. Direct determination of mercury species by X-ray absorption near edge spectroscopy (XANES) showed inorganic Hg compounds to prevail in all soils, being Cinnabar (HgS_red) and Corderoite (Hg₃S₂Cl₂) the main species. Nevertheless, more soluble mercury compounds, such as HgO and HgSO₄, have been also identified in significant proportion (from 6 to 20% of total mercury content), indicating a potential risk of mercury mobilisation. On the other hand, the application of sequential extraction schemes (SES) revealed large portions of weakly available Hg extracted in the residual fraction, while Hg associated to the exchangeable phase amounts as much as 19% of total Hg, thus, supporting the results obtained by XANES.Finally, synchrotron-based micro X-ray fluorescence (μ-XRF) was applied to identify qualitative trends on elemental associations in sample particles through a systematic mapping of its surface. In this concern, results show a well-defined correlation between Hg and Cu/Ni in the analysed particles. On the other hand, an absence of correlation between Hg and several other elements (Fe, Ti, Ca, Zn, Mn and S) was also observed. These effects have been attributed to chemical and physical interactions of mercury species on both enriched particles and sample matrices.     

Direct determination of Hg in polymers by solid sampling-graphite furnace atomic absorption spectrometry : A comparison of the performance of line source and continuum source instrumentation

This work explores the potential of solid sampling-graphite furnace atomic absorption spectrometry (SS-GFAAS) for the fast and direct determination of Hg in polymers. Eight certified reference materials with different composition (polyethylene-PE-, polystyrene-PS-, poly vinyl chloride-PVC- and acrylonitrile butadiene styrene-ABS-) were selected for the study, covering a wide Hg content range (from 20 to 1100 μg g^− 1).     

Development of a gas chromatography-mass spectrometry method for the determination of pesticides in gaseous and particulate phases in the atmosphere

A reliable multi-residue method for determining gaseous and particulate phase pesticides in atmospheric samples has been developed. This method, based on full scan gas chromatography–mass spectrometry (GC–MS), allowed the proper determination of sixteen relevant pesticides, in a wide range of concentrations and without the influence of interferences. The pesticides were benfluralin, bitertanol, buprofezin, chlorfenvinphos, chlorpyrifos, chlorpyrifos-methyl, ethalfluralin, fenthion, lindane, malathion, methidathion, propachlor, propanil, pyriproxifen, tebuconazol and trifluralin. Comparisons of two types of sampling filters (quartz and glass fibre) and four types of solid-phase cartridges (XAD-2, XAD-4, Florisil and Orbo-49P) showed that the most suitable supports were glass fibre filter for particulate pesticides and XAD-2 and XAD-4 cartridges for gaseous pesticides (>95% recovery). Evaluations of elution solvents for ultrasonic-assisted extraction demonstrated that isooctane is better than ethylacetate, dichloromethane, methanol or a mixture of acetone:hexane (1:1).Recovery assays and the standard addition method were performed to validate the proposed methodology. Moreover, large simulator chamber experiments allowed the best study of the gas-particle partitioning of pesticides for testing the sampling efficiency for the validation of an analytical multiresidue method for pesticides in air. Satisfactory analytical parameters were obtained, with a repeatability of 5 ± 1%, a reproducibility of 13 ± 3% and detection limits of 0.05–0.18 pg m⁻³ for the particulate phase and 26–88 pg m⁻³ for the gaseous phase. Finally, the methodology was successfully applied to rural and agricultural samples in the Mediterranean area.