Antimony as a traffic-related element in size-fractionated road dust samples collected in Buenos Aires

The growing interest of public opinion in environmental problems conducted us to investigate the levels of a toxic traffic-related element such antimony in 19 size-fractionated street dust samples. Samples were collected in the megacity of Buenos Aires during two months at 19 sites with different urban characteristics and traffic profile. Samples were sieved in four fractions (F1 < 37 µm, F2: 37-55 µm, F3: 55-75 µm and F4: 55-100 µm) before elemental analysis. A mixture of aqua regia and hydrofluoric acid was used to digest all samples. Antimony concentrations were quantified by inductively coupled plasma optical emission spectrometry (ICP OES) or flow injection hydride generation-atomic absorption spectrometry (FI-HG-AAS).Twenty four out of 73 sub-samples analyzed showed Sb levels < 0.05 µg g^− 1; in the rest of the samples mean Sb concentrations varied from 1.4 to 20.4 µg g^− 1. Maximum and minimum concentrations (in µg g^− 1) found in individual samples in the four fractions were: Fraction 1, < 0.05-20.4; Fraction 2, < 0.05-18.4; Fraction 3, < 0.05-6.3; Fraction 4, < 0.05-7.7.Antimony was found to be enriched in the smallest size fraction of road dust, with mean enrichment factors varying between 27 (F3) and 272 (F1). Concentrations of Sb were correlated with those of other traffic-related elements such as Cu and Pb and higher levels were found in areas with medium and high traffic densities.     

Determination of Silicate by Hollow Cathode Glow Discharge-Atomic Emission Spectrometry with Hydride Generation Technique

Abstract

Hollow cathode glow discharge atomic emission spectrometry has been applied to the determination of silicon coupled with a novel gaseous hydride generation technique, involving drying of an aqueous solution of silicate (sample) and mixing with powdered LiAlH₄. Sample introduction into the glow discharge chamber was performed via a pinhole at the center of the cathode which was connected to the hydride generator. The detection limit for silicon was 6μg at 288.1 nm and 30 μg at 251.6 nm.

     

Determination of selenomethionine by high performance liquid chromatography-direct hydride generation-atomic absorption spectrometry

A simple, reliable, trace determination of selenomethionine (Semet) based on a direct hydride generation atomic absorption spectrometric method was developed using sodium tetrahydroborate (0.3% in 0.2% NaOH) and hydrochloric acid (3 M). The method excluded any chemical pretreatment prior to hydride generation (HG). The optimized HG system was successfully coupled with the HPLC system. The detection limit (3σ of blank; n=5), reproducibility (R.S.D. of three successive analyses/day, performed on three different days), and repeatability (R.S.D. of three successive analyses) of the method were 1.08 ng ml⁻¹, 9.8% for 9.04 ng ml⁻¹ and 2.1–9.5% for 30.0–1.27 ng ml⁻¹ Semet as Se (standards prepared in Milli-Q water). Calibration graph was linear up to 30 ng ml⁻¹. This HPLC-HG-AAS method is very promising and successfully determined Semet (spiked) in human urine.     

Reversible Hydrogen Uptake/Release over a Sodium Phenoxide–Cyclohexanolate Pair

Hydrogen uptake and release in arene–cycloalkane pairs provide an attractive opportunity for on‐board and off‐board hydrogen storage. However, the efficiency of arene–cycloalkane pairs currently is limited by unfavorable thermodynamics for hydrogen release. It is shown here that the thermodynamics can be optimized by replacement of H in the ‐OH group of cyclohexanol and phenol with alkali or alkaline earth metals. The enthalpy change upon dehydrogenation decreases substantially, which correlates with the delocalization of the oxygen electron to the benzene ring in phenoxides. Theoretical calculations reveal that replacement of H with a metal leads to a reduction of the HOMO–LUMO energy gap and elongation of the C?H bond in the α site in cyclohexanolate, which indicates that the cyclohexanol is activated upon metal substitution. The experimental results demonstrate that sodium phenoxide–cyclohexanolate, an air‐ and water‐stable pair, can desorb hydrogen at ca. 413 K and 373 K in the solid form and in an aqueous solution, respectively. Hydrogenation, on the other hand, is accomplished at temperatures as low as 303 K.     

Synthesis of Bimetallic Copper‐Rich Nanoclusters Encapsulating a Linear Palladium Dihydride Unit

The structurally precise Cu‐rich hydride nanoclusters [PdCu₁₄H₂(dtc/dtp)₆(C≡CPh)₆] (dtc: di‐butyldithiocarbamate ( 1 ); dtp: di‐isopropyl dithiophosphate ( 2 )) were synthesized from the reaction of polyhydrido copper clusters [Cu₂₈H₁₅(S₂CNⁿBu₂)₁₂]⁺ or [Cu₂₀H₁₁{S₂P(OⁱPr)₂}₉] with phenyl acetylene in the presence of Pd(PPh₃)₂Cl₂. Their structures and compositions were determined by single‐crystal X‐ray diffraction and the results supported by ESI‐mass spectrometry. Hydride positions in 1 were confirmed by single‐crystal neutron diffraction. Each hydride is connected to one Pd⁰ and four Cu^I atoms in slightly distorted trigonalbipyramidal geometry. The anatomies of clusters 1 and 2 are very similar and DFT calculations allow rationalizing the interactions between the encapsulated [PdH₂]^2? unit and its Cu₁₄ bicapped icosahedral cage. As a result, Pd has the highest coordination number (14) so far recorded.     

流动注射-氢化物发生-原子荧光光谱仪数学模型优化研究

流动注射-氢化物发生-原子荧光光谱法由于具有灵敏度高、测量范围宽、分析速度快等很多优点,在卫生、环保、地质、冶金等行业得到了广泛应用。但是,影响氢化物发生-原子荧光光谱仪灵敏度和谱峰展宽的因素很多,一般都是通过多次实验寻找最佳实验条件,实验条件的优化比较困难。针对这一问题,根据氢化物发生化学反应的特点以及检测系统的组成原理,利用质量守恒等物理定律,提出了一个测试系统的数学模型,建立了各实验参数与仪器灵敏度和谱峰展宽系数之间的函数关系,以对-氨基苯胂酸标准品的测试为例,通过理论仿真与实验结果相比较,证明这个模型能很好的模拟实验系统。最后,利用提出的数学模型,本文给出了各参数与灵敏度和谱峰展宽的关系图,提出气液分离器的容积、载流流速和进样体积是影响系统灵敏度和谱峰展宽的主要因素,利用这个关系图,综合调整三个参数,可以使灵敏度提高到原来的2.9倍,谱峰展宽缩小到原来的0.76,为优化实验条件提供了理论指导。     

氢化物发生-催化共振瑞利散射光谱法测定痕量砷

在硫酸介质中,以硼氢化钠(NaBH₄)为还原剂,可将As(Ⅲ)还原为砷化氢(AsH₃)气体使其逸出,用Ce(SO₄)₂-H₂SO₄-KI混合液做吸收液,在催化剂KI存在下四价铈与AsH₃气体反应生成具有共振瑞利散射(RRS)的砷微粒和具有荧光的三价铈,导致体系在370 nm处的RRS信号和在351 nm处的荧光强度增大。在选定条件下,As(Ⅲ)浓度分别在0.006～0.76 mg·L-1和0.006～0.28 mg·L-1范围内与RRS增加值ΔI和荧光强度增大值ΔF₃₅₁呈线性关系,检出限均为3.0 μg·L-1。据此可建立新的检测As(Ⅲ)的催化RRS和荧光光谱法。     

基于复合腔的波长可调谐连续橙红色激光器

设计并研制了一种基于复合腔结构的波长可调谐、瓦级连续输出的橙红色激光器.该激光器是由半导体激光侧泵Nd∶GdVO_4晶体产生p-偏振1 062.9nm基频光的谐振腔和使用周期性极化晶体MgO∶PPLN(三个极化周期为29.0μm、29.8μm和30.8μm)的单共振光学参量振荡器组成.在两个谐振腔的重叠区域,利用Ⅱ类临界相位匹配KTP晶体对s-偏振信号光与p-偏振1 062.9nm基频光进行腔内和频.通过对MgO∶PPLN晶体进行三个不同极化周期的调谐和30℃~200℃范围内的温度调谐,在三个波段(613.4~619.2nm@29.0μm、620.2~628.9nm@29.8μm和634.4~649.1nm@30.8μm)获得了波长可调谐的橙红色激光连续输出,并在相应波段(3 980.0~3 758.5nm@29.0μm、3 714.2~3 438.3nm@29.8μm和3 278.0~2 940.2nm@30.8μm)获得了波长可调谐的中红外闲频光的连续输出.在30℃最低调谐温度,通过改变晶体的极化周期,在613.4nm、620.2nm和634.4nm处测得最大连续输出功率分别为1.52 W、2.21 W和3.03 W,对应的三束闲频光最大连续输出功率分别为2.36 W@3 980.0nm、3.17 W@3 714.2nm和4.13 W@3 278.0nm.     

干法灰化-原子荧光光谱法测定植物样中痕量锗

锗是对人体有益的重要稀有元素,但锗在植物样中含量很低。目前锗的前处理方法主要采用湿法消解和微波消解两种,以上的前处理方法试剂用量大,称样量小,检出限难以满足植物样中锗的分析要求。氢化物发生-原子荧光光谱法测定锗等易形成共价氢化物的元素相对其他的方法具有明显的优势。为降低测定植物样中锗的检出限,准确测定植物中的锗。实验采用干法灰化法对植物样中锗进行富集,建立了植物样中痕量锗的氢化物发生-原子荧光光谱测定方法。实验了温度对植物样灰化的影响,结果表明,即使温度高达900 ℃也不会造成锗的挥发损失,进一步试验表明在600 ℃灼烧4 h,即可将植物样灰化完全。实验了灰化后样品的消解方法,确定了灰化后样品采用硝酸、氢氟酸和硫酸进行分解。采用大称样量高温灰化减少了试剂用量,有效降低了方法检出限,改善了方法精密度。方法检出限达到0.27 ng·g-1,方法精密度(RSD)在3.99%～6.81%,经生物国家一级标准物质验证方法准确可靠。     

Magnetic properties of Ho1−xMmxCo2 (x=0, 0.1, 0.2, 0.3 and 0.4) alloys and their hydrides

The influence of Mm (Mm=mischmetal) substitution and hydrogen absorption on the magnetic properties of Ho_1−xMm_xCo₂ (x=0, 0.1, 0.2, 0.3 and 0.4) alloys have been determined through the temperature dependence of ac susceptibility and thermopower measurements. The changes in magnetic-ordering temperature of Ho_1−xMm_xCo₂ alloys have been explained based on the dilution of the magnetic ions and weakening of 4f–3d exchange interactions. The gradual disappearance of the magnetic transition temperature upon increasing hydrogen concentration (y) has been interpreted by the lattice expansion and charge transfer between absorbed hydrogen and 3d-band of Ho_1−xMm_xCo₂.