原位微区同步辐射X射线荧光和近边吸收谱研究铅耐受细菌吸附-转化铅机理

为了从微观水平研究细菌生物吸附及转化铅机理,利用原位微区同步辐射X射线荧光(μ-SRXRF)及X射线吸收近边结构谱( XANES)研究云南兰坪铅锌矿区农田土壤样品中筛选的铅耐受性细菌吸附铅的分布特征及铅形态转化规律。土壤中具有铅耐受性的菌株主要为Arthrobacter sp.属(节杆菌属),采用μ-SRXRF对其吸附铅的含量进行快速简单直接分析,部分细菌吸附铅的含量高达5925μg/g,富集系数达14.8。XANES结果表明,细菌吸附 Pb 后存在形态为 PbS、(C17 H35 COO)2Pb 和 Pb5(PO4)3Cl 分别占58.0％,22.2％和19.8％,与培养基本身以有机态为主的Pb形态有明显差异,表明培养基中铅被细菌吸附后有向硫化物转化的趋势,这为研究重金属生物有效性的影响因素提供了实验参考。     

Novel coated-graphite membrane sensor based on N,N′-dimethylcyanodiaza-18-crown-6 for the determination of ultra-trace amounts of lead

A novel selective membrane electrode for determination of ultra-trace amount of lead was prepared. The PVC membrane containing N,N′-dimethylcyanodiaza-18-cown-6 (DMCDA18C6) directly coated on a graphite electrode, exhibits a Nernstian response for Pb²⁺ ions over a very wide concentration range (from 1.0×10⁻² to 1.0×10⁻⁷ M) with a limit of detection of 7.0×10⁻⁸ M (∼14.5 ppb). It has a fast response time of ∼10 s and can be used for at least 2 months without any major deviation in potential. The electrode revealed very good selectivity with respect to all common alkali, alkaline earth, transition and heavy metal ions. The proposed sensor was used as an indicator electrode in potentiometric titration of lead ions and in determination of lead in edible oil, human hair and water samples. The proposed sensor was found to be superior to the best Pb²⁺-selective electrodes reported in terms of detection limit and selectivity coefficient.     

Characteristics of subtractive anodic stripping voltammetry of Pb and Cd at silver and gold electrodes

Silver and gold electrodes are useful for the quantitative determination of lead and cadmium with subtractive anodic stripping voltammetry (SASV). The use of SASV is essential for achieving good separation between the two peaks, to eliminate the interference of nitrates when cadmium is present and to allow analysis at very low concentrations without the removal of oxygen. The deposition and dissolution of Pb²⁺ and Cd²⁺ proceed at underpotential (UPD) on both electrodes. The UPD properties of the deposits are the main factor determining the analytical characteristics of the ASV method and are strongly affected by the type and concentration of the electrolyte. The effects of anions (Cl⁻, Br⁻, SO₄²⁻, NO₃⁻) and acids (HNO₃, HClO₄, H₂SO₄, HCl) are shown. The two electrodes complement each other and, in addition, enable the qualitative identification of Pb²⁺ and Cd²⁺, since the peaks appear in opposite order on the two electrodes. Analysis of mixtures of the two analytes is restricted on gold but not on silver. At gold the two peaks overlap: (i) at concentrations of cadmium higher than 250 nM at deposition times greater than 30 s, (ii) in the presence of copper at concentrations higher than 1 μM, and (iii) in the presence of Triton X-100 at concentrations above 10 mg/l. The repeatability at 10 nM analyte is better than 2.5%. The detection limits for Pb²⁺ and Cd²⁺ at 120 s deposition time and 3500 rpm rotation rate are: dl_Pb/Ag=0.04 nM; dl_Cd/Ag=0.7 nM; dl_Pb/Au=0.1 nM; dl_Cd/Au=0.3 nM. The analysis of lead and cadmium in natural waters has been performed.     

Distribution of Helium Isotopes in Western Pacific Upper Layer

3He/4He ratios in samples of sea water obtained at depths from surface to 300 m in the upper layer of the Western Pacific Ocean were measured by a mass spectrometer VG5400. The lateral and vertical distribution of He isotopes in the studied area was discussed in detail on the basis of 3He/4He ratios. Excess and depleted 3He. in relation to δ3He value of surface water in equilibrium with air has been discussed in the area, which may be mainly attributed to the incorporation of the North Pacific Intermediate Water with the Equatorial Upwelling and the exchange of water masses between the South China Sea and the Western Pacific, respectively. The present work in Western Pacific has also indicated that He isotopes may be used as a tracer for mixing processes of water masses and oceanic circulation.     

含铅聚合物微凝胶与硫化氢反应前后在良溶剂中的分子扩散行为

用溶液聚合法制备出轻度交联的含铅微凝胶,用光子相关光谱技术测定其在良溶剂中与H₂S反应前、后的扩散行为,由外推法得到在浓度无限稀时的分子扩散系数,给出微凝胶的流体力学半径。结果表明:相同量的含铅微凝胶在不同的初始浓度下与H₂S反应,生成含PbS纳米微粒的凝胶;但其体积增大不同,这说明H₂S与含铅微凝胶的反应既可以在分子内也可以在分子间进行,分子间的反应使含硫化铅微凝胶扩散系数随浓度的变化曲线的线性范围变小。     

Environmental exposure to metals of newborns, infants and young children

Anthropogenic emissions, such as those from combustion of fossil fuel, waste incineration and industrial use, contribute to higher levels of metal pollutants, including Cd, Pb and Sb, in the urban environment. These widespread and persistent environmental pollutants have the potential for developmental and reproductive toxicity. Health risks are particularly associated with exposure in utero and the early years of life, since the developing organism is at greater risk from permanent damage, and both absorption and retention can be considerably greater in infants than adults. In order to assess risk to humans, the information on environmental levels of pollutants (environmental monitoring) should be integrated with information on biomarkers of exposure, effect or susceptibility in biological fluids or tissues (biological monitoring). The analysis of tissue from the target organ obtained at autopsy provides a direct record of the accumulation of toxins and allows temporal and geographical trends to be studied. Few literature reports on tissue content of potentially toxic elements include data on newborns and young children since collections of autopsy samples in this age range are rare. Existing data are sometime questionable, because of inadequate sensitivity of the analytical techniques, insufficient control of contamination and lack of validation. Our recent work aimed to establish reliable reference values for the content of Cd, Pb and Sb in the liver of pediatric subjects.     

生物,环境样品和食品中铅的痕量分析

主要根据近七年来发表的有关论文，综述了我国生物、环境样品和食品中铅和痕量分析技术进展，内容包括分子光谱、原子光谱、电化学和其他分析方法，以及联用技术和前处理等方面，收集文献３９３篇。     

On-line pretreatment and determination of Pb, Cu and Cd at the μg l level in drinking water by chelation ion chromatography

A novel, highly sensitive method for the simultaneous separation and determination of lead, copper, cadmium and other transition metals in drinking water was achieved by on-line sample pretreatment of chelation ion chromatography. Manganese, which coeluted with cadmium, was oxidized to permanganate by ammonium persulfate before injection. Permanganate, with bulk quantity of alkali, alkaline earth metals, iron and aluminum, was eliminated by pyrophosphoric acid–ammonium acetate buffer solution (pH 5.5), while retaining heavy and transition metals on a selective chelating resin (MetPac CC-1 column). Then, they were disabsorbed and transferred to a sulfonated cation exchanger (TMC-1 column). Finally, the concentrated trace metals were separated on a bifunctional ion-exchange column (CS5A) by a concentration gradient of oxalic acid and sodium nitrate eluents, coupled with post-column spectrophotometric detection with 2-[(5-bromo-2-pyridyl)azo]-5-diethylaminophenol (5-Br-PADAP) at 560 nm. The separation and color-development conditions were optimized. The detection limits for the method (signal-to-noise ratio=3:1) were at or below the μg l⁻¹ level. The results of drinking water analyses were satisfactory.     

Tunable UV generation at 283 nm by frequency doubling and sum frequency mixing of two semiconductor lasers for the detection of Pb

High resolution atomic absorption measurements of lead at 283 nm in a vapor cell were performed by frequency doubling an 850 nm laser diode to obtain 425 nm light, followed by sum frequency generation of the harmonic radiation with a second 850 nm laser diode.     

Lead ion selective PVC membrane electrode based on 5,5'-dithiobis-(2-nitrobenzoic acid)

A PVC membrane electrode for lead ions based on 5,5′-dithiobis-(2-nitrobenzoic acid) as membrane carrier was prepared. The electrode exhibits a Nernstian response for Pb²⁺ over a wide concentration range (1.0×10⁻²–4.0×10⁻⁶ M). It has a relatively fast response time and can be used for at least 3 months without any divergence in potentials. The proposed electrode revealed good selectivities for Pb²⁺ over a wide variety of other metal ions and could be used in a pH range of 2.0–7.0. It was used as an indicator electrode in potentiometric titration of lead ions and in direct determination of lead in water samples.