Laboratory intercomparison study on the analysis of short-chain chlorinated paraffins in an extract of industrial soil

Short-chain chlorinated paraffins (SCCPs) comprise a class of organic pollutants used in many industrial applications and released into the environment. The analytical determination of SCCPs is very challenging. Although there is at present no fully validated measurement procedure that might be applied in routine monitoring, the European Union Water Framework Directive (WFD) has required regular monitoring of this class of compounds at river-basin scale since 2007.To assess the status quo of the analysis of SCCPs in relation to the requirements of the WFD, we organized an interlaboratory comparison on the quantification of SCCPs in an extract of an industrial soil. Six laboratories participated in the exercise using three different techniques [i.e. gas chromatography (GC) coupled to mass spectrometry (MS) in electron-capture negative ionization mode, GC with atomic emission detection, and carbon-skeleton GC-MS]. The results reported were in the range 8.5–3200 mg/L. This confirms that reliable quantification of SCCPs is still very difficult to achieve and that the comparability of SCCP data reported to the European Commission is at least questionable.     

鞘氨醇与DPPC, DPPE单层膜的热力学特性及形态观察

鞘氨醇(sphingosine)是生物体内合成鞘脂的母体化合物, 是生物膜中的重要组分之一. 通过分析表面压力和平均分子面积(π-A)等温线数据分别研究了鞘氨醇与二棕榈酰基磷脂酰胆碱(DPPC)和二棕榈酰基磷脂酰乙醇胺(DPPE)二元组分单层膜的热力学特性, 并在恒定膜压下制备不同摩尔比例的混合脂膜用原子力显微镜进行观测. 实验结果表明: (1)鞘氨醇与DPPC组成的系统中, XD-Sph＝0.2, 0.4, 0.6时, 过量分子面积与过量吉布斯自由能在所研究的表面压力下表现为负值, 而当XD-Sph＝0.8时, 表现为正值; (2)鞘氨醇与DPPE组成的系统中, 当表面压力 π＜25 mN•m－1时, 过量分子面积与过量吉布斯自由能在所研究的组分比例下表现为负值, 当π≥25 mN•m－1时为正值. 混合单层膜的分子面积与表面吉布斯自由能决定了分子间的相互作用, 当为负值时分子间相互作用表现为吸引力, 出现凝聚现象; 为正值时分子间相互作用表现为排斥力, 促使单层膜出现相分离现象. 过量吉布斯自由能值越小, 单层膜的热稳定性越高. 弹性系数曲线分析和AFM图片观测进一步验证了理论分析的结果.     

Fast sequential multi-element determination of Ca,Mg, K,Cu, Fe,Mn and Zn for foliar diagnosis using high-resolution continuum source flame atomic absorption spectrometry: Feasibility of secondary lines,side pixel registration and least-squares background correction

The fast sequential multi-element determination of Ca, Mg, K, Cu, Fe, Mn and Zn in plant tissues by high-resolution continuum source flame atomic absorption spectrometry is proposed. For this, the main lines for Cu (324.754 nm), Fe (248.327 nm), Mn (279.482 nm) and Zn (213.857 nm) were selected, and the secondary lines for Ca (239.856 nm), Mg (202.582 nm) and K (404.414 nm) were evaluated. The side pixel registration approach was studied to reduce sensitivity and extend the linear working range for Mg by measuring at wings (202.576 nm; 202.577 nm; 202.578 nm; 202.580 nm; 202.585 nm; 202.586 nm; 202.587 nm; 202.588 nm) of the secondary line. The interference caused by NO bands on Zn at 213.857 nm was removed using the least-squares background correction. Using the main lines for Cu, Fe, Mn and Zn, secondary lines for Ca and K, and line wing at 202.588 nm for Mg, and 5 mL min^− 1 sample flow-rate, calibration curves in the 0.1–0.5 mg L^− 1 Cu, 0.5–4.0 mg L^− 1 Fe, 0.5–4.0 mg L^− 1 Mn, 0.2–1.0 mg L^− 1 Zn, 10.0–100.0 mg L^− 1 Ca, 5.0–40.0 mg L^− 1 Mg and 50.0–250.0 mg L^− 1 K ranges were consistently obtained. Accuracy and precision were evaluated after analysis of five plant standard reference materials. Results were in agreement at a 95% confidence level (paired t-test) with certified values. The proposed method was applied to digests of sugar-cane leaves and results were close to those obtained by line-source flame atomic absorption spectrometry. Recoveries of Ca, Mg, K, Cu, Fe, Mn and Zn in the 89–103%, 84–107%, 87–103%, 85–105%, 92–106%, 91–114%, 96–114% intervals, respectively, were obtained. The limits of detection were 0.6 mg L^− 1 Ca, 0.4 mg L^− 1 Mg, 0.4 mg L^− 1 K, 7.7 µg L^− 1 Cu, 7.7 µg L^− 1 Fe, 1.5 µg L^− 1 Mn and 5.9 µg L^− 1 Zn.     

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).     

Determination of Copper and Zinc Ions by Flame-AAS After Preconcentraction Using Sodium Dodecyl Sulfate Coated Alumina Modified with 3-((1H-Indol-3-yl)-3,4,5-trimethyl)-1H-indole

A sensitive and simple method for the simultaneous preconcentration of trace amount Cu²⁺ and Zn²⁺ ions in some real samples has been established, which is based on the sorption of Cu²⁺ and Zn²⁺ on 3‐((1H‐indol‐3‐yl)‐3,4,5‐trimethyl)‐1H‐indole (ITMI) loaded on sodium dodecyl sulfate (SDS) coated alumina. The metal absorbed on the complexes was eluted using 3 mol/L nitric acid. The influences of the analytical parameters including pH and sample volume were investigated. The effects of matrix ions on the retentions of the analytes were also examined. The recoveries of analytes were generally higher than 95% with a low RSD. The method has been successfully applied to content evaluation of these metals in real samples.     

Hollow fiber liquid phase microextraction combined with electrothermal atomic absorption spectrometry for the speciation of arsenic (III) and arsenic (V) in fresh waters and human hair extracts

A new method of hollow fiber liquid phase microextraction (HF-LPME) using ammonium pyrrolidine dithiocarbamate (APDC) as extractant combined with electrothermal atomic absorption spectrometry (ETAAS) using Pd as permanent modifier has been described for the speciation of As(III) and As(V). In a pH range of 3.0-4.0, the complex of As(III)-APDC complex can be extracted using toluene as the extraction solvent leaving As(V) in the aqueous layer. The post extraction organic phase was directly injected into ETAAS for the determination of As(III). To determine total arsenic in the samples, first As(V) was reduced to As(III) by l-cysteine, and then a microextraction method was performed prior to the determination of total arsenic. As(V) assay was based on subtracting As(III) form the total arsenic. All parameters, such as pH of solution, type of organic solvent, the amount of APDC, stirring rate and extraction time, affecting the separation of As(III) from As(V) and the extraction efficiency of As(III) were investigated, and the optimized extraction conditions were established. Under optimized conditions, a detection limit of 0.12 ng mL⁻¹ with enrichment factor of 78 was achieved. The relative standard deviation (R.S.D.) of the method for five replicate determinations of 5 ng mL⁻¹ As(III) was 8%. The developed method was applied to the speciation of As(III) and As(V) in fresh water and human hair extracts, and the recoveries for the spiked samples are 86-109%. In order to validate the developed method, three certified reference materials such as GBW07601 human hair, BW3209 and BW3210 environmental water were analyzed, and the results obtained were in good agreement with the certified values provided.     

Crystal-chemical analysis of the structures of minerals with [Hg<Subscript>2</Subscript>]<Superscript>2+</Superscript> dumbbells

An analysis of the structures of minerals with [Hg₂]²⁺ dumbbells including poyarkovite [Hg₂]₃Cl₂O₂, shakhovite [Hg₂]₂Sb(OH)₃O₃, vasilyevite Hg₂₀O₆I₃Br₂Cl(CO₃), and kelyanite [Hg₂]₆[SbO₆]BrCl₂ was carried out. The determining factor in structure formation is the ordering of the centers of the cluster groups of mercury and large anions by systems of equidistant parallel planes with d _hkl ～ 2.5–4.5 Å. The different combinations of atoms and fragments in the structure are ordered by their own pseudotranslation lattices; this probably reflects the stages of crystallization. The crystal structures under study are examples of balance between the local interatomic interactions and the forces that create long-range order for different stoichiometries, masses, and sizes of components.     

Determination of beryllium by electrothermal atomic absorption spectrometry using tungsten surfaces and zirconium modifier

Electrothermal atomization of beryllium from graphite and tungsten surfaces was compared with and without the use of various chemical modifiers. Tungsten proved to be the best substrate, giving the more sensitive integrated atomic absorption signals of beryllium. Tungsten platform atomization with zirconium as a chemical modifier was used for the determination of beryllium in several NIST SRM certified reference samples, with good agreement obtained between the results found and the certified values. The precision of the measurements (at 10 μg L⁻¹), the limit of detection (3σ), and the characteristic mass of beryllium were 2.50%, 0.009 μg L⁻¹ and 0.42 pg, respectively.     

Taguchi OA16 orthogonal array design for the optimization of cloud point extraction for selenium determination in environmental and biological samples by tungsten-modified tube electrothermal atomic absorption spectrometry

Orthogonal array design (OAD) was applied for the first time to optimize cloud point extraction (CPE) conditions for Se(IV) determination by electrothermal atomic absorption spectrometry (ETAAS) in environmental and biological samples. Selenium was reacted with o-phenylenediamine to form piazselenol in an acidic medium (pH 2). Using Triton X-114, as surfactant, piazselenol was quantitatively extracted into small volume (about 30 μL) of the surfactant-rich phase after centrifugation. Five relevant factors, i.e. surfactant concentration, pH, ionic strength, equilibrium time and temperature were selected and the effects of each factor were studied at four levels on the extraction efficiency of Se(IV) and optimized. The statistical analysis revealed that the most important factors contributing to the extraction efficiency are ionic strength, pH and percent of surfactant. Based on the results obtained from the analysis of variance (ANOVA), the optimum conditions for extraction were established as: pH 6; vial temperature = 50 °C; extraction time = 7 min and 0.3% (w/v) of Triton X-114. The method was permitted to obtain a detection limit of 0.09 ng mL⁻¹ and two linear calibration ranges from 0.6 to 1.0 and 1.0 to 80.0 ng mL⁻¹ Se. The precision (%RSD) of the extraction and determination for the six replicates of Se at 20 ng mL⁻¹ was better than 3.6% and the enrichment factor of 63.5 was achieved. The studied analyte was successfully extracted and determined with high efficiency using cloud point extraction method in water and biological matrices.     

Application of tandem column solid phase extraction and flame atomic absorption spectrometry for the determination of inorganic and organically bound forms of iron in wine

A tandem column solid phase extraction (SPE) procedure has been devised to examine the fractionation of Fe in wine. Wine was filtered through a 0.45 μm filter and then, the filtrate was driven through an adsorbing Amberlite XAD-7HP column followed by a cation exchange Dowex 50W-x8-200 column. Three different Fe groupings are discriminated and assessed, including hydrophobic species of Fe bound to phenolic substances and related species (phenolic fraction), cationic species comprising simple Fe ions and labile Fe forms (cationic fraction), in addition to anionic and/or neutral Fe complexes with organic acids (residual fraction). The suitability of the procedure has been evaluated analyzing four bottled red wines. The results obtained were verified using another tandem column assemblage in which an adsorbing Amberlite XAD-16 column was exchanged by the Amberlite XAD-7HP column. The fractionation pattern ascertained for Fe in analyzed wines is discussed in reference to previously published works. In addition, a conditioning treatment and preparation of Amberlite XAD resins have been revised.