Estimation of platinum in environmental water samples with solid phase extraction technique using inductively coupled plasma mass spectrometry

A solid phase extraction technique for the determination of platinum(IV) at trace levels by inductively coupled plasma mass spectromA solid phase extraction technique for the determination of platinum(IV) at trace levels by inductively coupled plasma mass spectrometry (ICP-MS) was developed. The method was based on retention of platinum in a sample on silica gel modified with aminepropyl groups. The retention of platinum(IV) from the sample solution and the recovery of platinum with 1.0 mol L⁻¹ thiourea solution were quantitative. The relative standard deviation (RSD) was calculated as 5% (n = 7) at the 10 ng L⁻¹ level. The enrichment factor was found to be (50-fold) for 250 mL of water sample. Under optimum conditions, the method detection limit (MDL) was found to be 1 ng L⁻¹ for platinum in water matrices. Recoveries of Pt from spike addition to atmospheric water samples were quantitative (80–95%). The present method was used for the determination of platinum in precipitation, throughfall and runoff water samples.      

Stripping Analysis of Trace Metals at a Flow-Through Reticulated Vitreous Carbon Electrode after the Preconcentration by Supported Liquid Membrane Technique

Abstract

The performance of a flow-through mercury coated reticulated vitreous carbon (RVC) electrode in the potentiometric stripping analysis (PSA) of trace metals has been examined. A wall-jet glassy carbon cell was used for the comparative experiments. Experimental parameters influencing the stripping signals have been optimised in order to use the stripping analysis after the preconcentration and matrix isolation by supported liquid membrane (SLM) technique. The SLM with di-2-ethylhexyl-phosphoric acid (DEHPA) as the extractant in the membrane liquid for proton driven transport of trace metals across the membrane has been chosen. Results presented for lead determination in river water demonstrate the analytical advantages of coupled technique SLM-PSA.     

Removal of Mn(II) and Cd(II) from wastewaters by natural and modified clays

The adsorption capacities of commercial and Brazilian natural clays were evaluated to test their applications in wastewater control. We investigated the process of sorption of manganese(II) and cadmium(II) present in synthetic aqueous effluents, by calculating the adsorption isotherms at 298 K using batch experiments. The influence of temperature and pH on the adsorption process was also studied. Adsorption of metals was best described by a Langmuir isotherm, with values of Q ₀ parameter, which is related to the sorption capacity, corresponding to 6.3 mg g^{− 1} for K-10/Cd(II), 4.8 mg g^{− 1} for K-10/Mn(II), 11.2 mg g^{− 1} for NT-25/Cd(II) and 6.0 mg g^{− 1} for NT-25/Mn(II). We observed two distinct adsorption mechanisms that may influence adsorption. At the first 5 min of interaction, a cation exchange mechanism that takes place at exchange sites located on (001) basal planes is predominant. This process is inhibited by low pH values. After this first and fast step, a second sorption mechanism can be related to formation of inner-sphere surface complexes, which is formed at edges of the clay. The rate constants and the initial sorption rates correlate positively with temperature in all studied systems, denoting the predominance of a physisorption process. The addition of complexing agents that are incorporated within the K10 structure, enhance metal uptake by the adsorbent. The results have shown that both Cd(II) and Mn(II) were totally retained from a 50 mg L^{− 1} solution when K10 grafted with ammonium pyrrolidinedithiocarbamate (APDC) was used as adsorbent.     

Kinetic study of uranium speciation in model solutions and in natural waters using Competitive Ligand Exchange Method

Kinetic speciation of uranium in model solutions containing uranium and humic acid (HA) and in natural waters has been investigated by Competitive Ligand Exchange Method (CLEM). In alkaline freshwaters, most of uranium species were uranium-carbonate species, which were labile in the CLEM experiment. The uranium speciation of every sample was characterized either as “labile” or “non-labile” uranium complexes depending on the dissociation rate coefficients of the complexes. The results showed that as the U(VI)/HA ratio was decreased, the dissociation rate coefficients decreased and the labile fraction decreased as well. When the U(VI)/HA ratio was 0.1, the labile fraction of the U(VI)-HA increased with increasing pH; however, there was no pH effect on the dissociation of U(VI)-HA complexes at lower U(VI)/HA ratios. Chelex-100 had some limitations in its use for the study of dissociation of U(VI)-HA complex at very low U(VI)/HA ratios. By developing an analytical method and procedure for quantitative determination of kinetic parameters for the dissociation of uranium-HA complexes in model solutions and natural waters, this work has made a substantial contribution to analytical chemistry.     

Solid‐phase extraction and HPLC determination of fluoroquinolones in surface waters

An investigation on filtration procedures and SPE sorbents used for the determination of traces of the most common veterinary fluoroquinolones (FQs), marbofloxacin (MAR) and enrofloxacin (ENR) used as antibacterial agents in cattle and swine farms in the province of Pavia (Italy), was performed in natural waters. The filter composition and the sorbent used in the SPE strongly influence the correct recovery, both in terms of total and dissolved FQs concentration. An accurate comparison among different filters and SPE sorbents showed that a full determination of analytes was possible on nylon filters followed by anionic (WAX) and hydrophilic–lipophilic balance (HLB) resins as SPE. Quantitative analysis was done by chromatography with fluorescence detection (HPLC‐FD). Fluoroquinolones recovery was between 90 and 116% with RSD not greater than 10% (sample volume 250 mL). The developed method allowed to determine both dissolved and NOM‐absorbed fractions of FQs, therefore a full determination of the analytes was possible. Limits of detection (LOD) and quantification (LOQ) were, respectively, 0.7 and 2.2 ng/L for ENR and 2 and 6 ng/L for MAR. The kinetics of degradation under solar light was explored.     

Effects of various competing ligands on the kinetics of trace metal complexes of Laurentian Fulvic Acid in model solutions and natural waters

The objective of this work was to study the effects of the following Ligands: Chelex-100, Dowex MAC-3 and Dowex 50WX-8 using Competing Ligand Exchange Method. This objective was achieved by investigating complex dissociation kinetics of trace metals: Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Mn(II) and Pb(II) of a well-characterized Laurentian Fulvic Acid (LFA) in model solutions and in a natural waters of Lake Heva (Québec, Canada). The effects of variation in the competing ligands (including their quantities) on the complex dissociation kinetics were quantitatively characterized by their first-order dissociation rate coefficients. The kinetic lability of the metal complexes varied with the metal-to-LFA ratio, as expected from the theory of metal complexes of the chemically and physically heterogeneous complexants, LFA. The general trend in the metal-binding by the above competing ligands was: Dowex 50WX-8 > Chelex-100 > Dowex MAC-3. However, no difference was found between the Dowex 50WX-8 and Chelex-100 for Cd(II), Zn(II), and Co(II). The results revealed the importance of the quantity of Chelex-100 as a competing ligand in the metal(II)-LFA complexation, on the dissociation kinetics of these complexes in model solutions. By developing Competing Ligand Exchange Method as an analytical technique, for studying the relative affinities of the above competing ligands for metals complexation in natural waters this work has made a substantial contribution to analytical chemistry.     

Dual optoelectronic visual detection and quantification of spectroscopically silent heavy metal toxins: A multi-measurand sensing strategy based on Rhodamine 6G as chromo or fluoro ionophore

A novel colorimetric chemo-sensor for the simultaneous visual detection and quantification of spectroscopically silent heavy metal toxins viz. cadmium, lead and mercury has been developed. This is based on the proposed sequential ligand exchange (SLE) mechanism of iodide from Pb-I⁻-Rhodamine 6G ion associate with citrate (without affecting ion associates of Cd and Hg) and subsequently from Cd-I⁻-Rhodamine 6G ion associate with EDTA (without affecting Hg-I⁻-Rhodamine 6G). Multi-measurand detection and quantification by colorimetry is possible as the individual toxins gives identical bathochromic shifts in aqueous solution, i.e. from 530 to 575 nm on formation of ternary ion associates in singular, binary and ternary mixtures. The visual detection provides a simple, quick and sensitive detection method in addition to quantification via spectrophotometry with Sandell sensitivities of 1.1, 15 and 2.5 μg dm⁻² for cadmium, lead and mercury, respectively. The developed procedure has been successfully tested for the analysis of environmental (cast alkali, lead acid battery and zinc manufacturing industry effluents) samples. Furthermore, the multi-measurand quantification of the above-mentioned heavy metal toxins based on fluorescence quenching and use of Pyronine G as chromo-ionophore instead of Rhodamine 6G is also described.     

Multi-residue analysis and ultra-trace quantification of 36 priority substances from the European Water Framework Directive by GC-MS and LC-FLD-MS/MS in surface waters

A multi residue analysis was developed for screening, quantification and confirmation of 36 priority organic compounds included in the 2000/60/EC European Water Framework Directive. The compounds analyzed included 19 pesticides, 8 PAH, 5 endocrine-disruptors and 4 organochlorine compounds. The method was developed in three steps. First, automated off-line solid-phase extraction using Strata X cartridges was optimized to trap simultaneously the 36 studied compounds. Second, the more volatile compounds were analysed by gas chromatography coupled to mass spectrometry with electron impact ionisation in selected ion monitoring mode (SIM). Third, the last 20 compounds were detected and quantified, in one run, by liquid chromatography coupled to fluorescence detector and tandem mass spectrometry. The excellent selectivity and sensitivity allowed us satisfactory quantification and confirmation at levels as low as 0.2-67 ng L⁻¹ with recoveries between 59 and 105%. Such methodology was then applied to French surface waters: all the waters present organic contaminants, and their concentration varied according to the origin and nature of substances.     

Kinetic Determination of Iodide Based on its Effect on the Hydrogen Peroxide Oxidation of Triflupromazine

Summary.  A new selective, sensitive, and simple kinetic method is developed for the determination of trace amounts of iodide. The method is based on the catalytic effect of iodide on the reaction of triflupromazine (TFP) with H₂O₂. The reaction is followed spectrophotometrically by tracing the oxidation product at 498 nm within 1 min after addition of H₂O₂. The optimum reaction conditions are TFP (0.4 × 10⁻³ M), H₂SO₄ (1.0M), H₃PO₄ (2.0M), and H₂O₂ (1.6M) at 30°C. Following this procedure, iodide can be determined with a linear calibration graph up to 4.5 ng ċ cm⁻³ and a detection limit of 0.04 ng ċ cm⁻³, based on the 3 S_b criterion. The method can also be applied to the determination of iodate and periodate ions. Determination of as little as 0.2, 1.0, 2.0, and 4.0 ng ċ cm⁻³ of I⁻, IO₃ ^-, or IO₄ ^- in aqueous solutions gave an average recovery of 98% with relative standard deviations below 1.6% (n = 5). The method was applied to the determination of iodide in Nile river water and ground waters as well as in various food samples after alkaline ashing treatment. The method is compared with other catalytic spectrophotometric procedures for iodide determination. Received January 19, 2001. Accepted (revised) March 12, 2001     

大理岩动态拉伸强度及弹性模量的SHPB实验研究

提出了获取脆性材料动态拉伸强度及弹性模量的实验步骤及相关记录数据的分析方法。利用直径为100mm的分离式Hopkinson压杆径向冲击巴西圆盘和平台巴西圆盘试样,测试了大理岩在高应变率加载下的动态力学性能。应力波加载下动态劈裂拉伸圆盘在试样中心产生了约45/s的拉伸应变率。分析了实验的有效性并考虑了试样两个端面应力波波形差异的影响以提高实验结果的精度。结果表明准静态下的公式可适用于动态劈裂拉伸实验;大理岩的动态拉伸强度及弹性模量比静态时有明显的增加。