Determination of titanium in sea water using catalytic cathodic stripping voltammetry

Titanium(IV) dissolved in sea water can be determined using adsorptive cathodic stripping voltammetry in the presence of mandelic acid. The method is improved by the addition of chlorate to the sample, which causes the peak current to increase by more than an order of magnitude owing to the reoxidation of the Ti(III) (mediated by the chlorate), which was produced at the electrode surface during the potential scan, to Ti(IV), where it again contributed to the reduction current. The sensitivity of the voltammetric technique was thus improved by a factor of 20, and the limit of detection was lowered to 7 pM with 60 s adsorption (ca. 1 pM with 600 s adsorption), sufficiently low to determine titanium in water of oceanic origin. The method was applied to the determination of titanium in the estuary of the River Mersey. The titanium concentration was found to vary between 0.2 and 0.3 nM (at salinities of 32–33) and 1.5 nM (at salinities of 1–4), revealing a conservative behaviour at salinities above 20 and some removal at low salinities.     

Platinum,Rhodium, Palladium and Lead: Elements Linked to Vehicle Emissions. Their Simultaneous Voltammetric Determination in Superficial Water

The present work, regarding the determination of Pt(II), Rh(III) by square‐wave adsorption stripping voltammetry (SWAdSV), Pd(II) by square‐wave voltammetry (SWV) and Pb(II) by square‐wave anodic stripping voltammetry (SWASV) in superficial water is an interesting example of the possibility to simultaneously, or better sequentially determine each single element in real samples. The critical comparison between peak area and peak current highlights that lower limits of detection are obtained if peak area is employed as instrumental datum. 0.6 mmol/L formaldehyde+1.2 mmol/L hydrazine (formazone complex) in 0.3 mol/L HCl and ammonia‐ammonium chloride buffer pH 9.6 were employed as the supporting electrolytes. The analytical procedure was verified by the analysis of the standard reference materials: Sea Water BCR‐CRM 403 and Fresh Water NIST‐SRM 1643d. Precision and accuracy, expressed as relative standard deviation and relative error, respectively, were generally lower than 6% in all cases. Once set up on the standard reference materials, the analytical procedure was transferred and applied to superficial water sampled in proximity to superhighway and in the Po river mouth area. A critical comparison with spectroscopic measurements is also discussed.     

Optimization of smoothing process-the method to improve calibration in voltammetry Part I. Simulated voltammograms

The problem of the optimal choice of algorithmic filter and the evaluation of smoothing effects in voltammetry is studied. The basic idea of the optimization is an investigation of the improvement of the calibration and the recovery functions parameters during denoising process. The evaluation routine yields the answer in numerical form and may be used for the best filter selection. In order to show how the proposed criterion operates, it was applied to the simulated curves which were peak shaped and distorted by noise of different type and amplitude. Results were compared to the other method based on difference between true and denoised signal. The described tool may be applied for the automatic signal processing.     

Identification of lead pigments in nanosamples from ancient paintings and polychromed sculptures using voltammetry of nanoparticles/atomic force microscopy

Voltammetry of nanoparticles coupled with atomic force microscopy was used to identify lead pigments in nanosamples proceeding from works of art. Upon mechanical attachment of few nanograms of sample to a graphite plate, well-defined voltammetric responses were obtained for lead orange, lead yellow, lead white, litharge, minium, Naples yellow, and tin-lead yellow, allowing for an unambiguous identification of such pigments. Atomic force images provide evidence for the occurrence of pigment-characteristic reduction processes accompanied by metal deposition on the graphite substrate. Electrochemical parameters are used for pigment identification. Application to the method for identifying lead pigments in different model binder + pigment specimens and pictorial samples from the canvas painting collection (anonymous, 17th century) of the Saint Joseph Church in Taormina (Italy), the frescoes painted by Antonio Acisclo Palomino y Velasco (1698) in the vault of the Sant Joan del Mercat church in València (Spain) and an anonymous polychromed sculpture (16th century) representing a Martyr Saint from Alacant (Spain) is described.     

Sensitive electrochemical detection of arsenic (III) using gold nanoparticle modified carbon nanotubes via anodic stripping voltammetry

Gold nanoparticles were deposited electrolessly on multiwalled carbon nanotubes (CNTs) via in situ reduction of HAuCl₄ by NaBH₄. The resulting gold covered nanotubes were immobilised onto the surface of a glassy carbon electrode via evaporation of a suspension in chloroform. Anodic stripping voltammetry was performed with the modified electrode in As(III) solutions. A limit of detection (LOD based on 3σ) of 0.1 μg L⁻¹ was obtained but more importantly a sensitivity of 1985 μA μM⁻¹ was obtained with square wave voltammetry (SWV) in an optimised system with a deposition time of 120 s. These values, particularly the high sensitivity compare favourably with previously reported methods in the area of electrochemical arsenic detection.     

A study by voltammetry and the photocurrent response method of copper electrode behavior in acidic and alkaline solutions containing chloride ions

The electrochemical behavior of Cu electrodes in Cl⁻ solutions was studied in a wide range of pH. The results were compared with those obtained in solutions containing F⁻, Br⁻, I⁻ and So²⁻₄ ions at pH 8.5, and discussed in terms of the competitive formation of Cu₂O and CuCl films on the Cu surface and the influence of CuCl on the properties of Cu₂O. At pH 8.5 or higher, Cu₂O was formed first, whereas at pH 5.7 or lower the Cu₂O film was formed on the Cu surface under the CuCl layer which was formed initially. It is believed that the Cu₂O films doped with Cl⁻ ions exhibited poor protective properties against Cu corrosion.     

Extending the dynamic range of copper determination in differential pulse adsorption cathodic stripping voltammetry using wavelet neural network

A wavelet neural network (WNN) model is proposed for extending the dynamic range of Cu(II) determination by differential pulse adsorption cathodic stripping voltammetry (DP-AdSV) using xylenol orange (XO) as a suitable ligand. All of voltammograms data consisting of Cu(II) and Cu(II)–XO peak currents were used in WNN model. The WNN model consisted of three layers (2-8-1) with the Morlet mother wavelet transfer function in the hidden layer. The model was able to extend the dynamic range of Cu(II) from its narrow linear range (1–50 ng ml⁻¹) to the higher dynamic range (1–1500 ng ml⁻¹). The results of the WNN model was also compared with artificial neural network (ANN) model and it was demonstrated the superiority of the WNN model relative to ANN model.     

Refreshable mercury film silver based electrode for determination of chromium(VI) using catalytic adsorptive stripping voltammetry

The refreshable mercury film silver based electrode Hg(Ag)FE applied for determination of Cr(VI) traces using catalytic adsorptive striping voltammetry (CAdSV) will be presented. The film electrode is characterized by its very good surface reproducibility (not less than 2%) and long-term stability (1500–2000 measurement cycles). The mechanical refreshing of mercury film is realized in the specially constructed device, in a time shorter than 1–2 s.

In the paper, it will be proved that a mechanically weak hanging mercury drop electrode (HMDE) may be substituted by mercury film Hg(Ag)FE electrode with a surface area adjustable from 1.5 to 12 mm². For the electrode surface 4 mm² the detection limit obtained for Cr(VI) was 0.19 nM, while the linearity range measured for a 20 s accumulation time was between 0.5 and 50 nM. The relative standard deviation (R.S.D.) in determination of Cr(VI) varied from 1 to 5%. The influence of the excess of Cr(III) on determination of Cr(VI) was analyzed using samples from the Dobczyce reservoir spiked with known amounts of Cr(VI) and Cr(III).     

Analytical and mineralogical studies of ore and impurities from a chromite mineral using X-ray analysis, electrochemical and microscopy techniques

A wide analytical study of South African chromite ore, material with high interest in ceramic industry, has been carried out. With this purpose, an accurate chemical identification and mineralogical characterization of the mineral and the gangue have been performed using X-ray fluorescence (XRF), voltammetry, X-ray diffraction (XRD), light microscopy (LM), and scanning electron microscopy (SEM/EDX). The elemental composition of the sample (ore and gangue) has been obtained by XRF. The voltammetric analysis has allowed to demonstrate that iron in the sample was as Fe(II). The main compound of the chromite ore was a spinel (magnesiochromite ferroan), identified by XRD from the sample, which constitutes the chromite ore. This technique has also been useful to characterize some silicates as impurities in the chromite ore sample. Light microscopy has allowed the detection of the spinel and the identification of a silicate impurity (chrome chlorite), by means of their colouration. On the other hand, the other silicate impurity was identified as labradorite by means of X-ray microscopy by SEM/EDX. Finally, a strategy was developed to calculate the composition of each mineral in the unknown sample. The obtained results were: chromite spinel 82.89%, chlorite 12.79% and labradorite 4.32%.     

Chemometrics assisted resolving of net faradaic current contribution from total current in potential step and staircase cyclic voltammetry

Total current in the electroanalytical data is assumed to be consisting of three main constituents: faradaic current, step charging current and induced charging current. Both charging currents can cause an interfering effect on precise determination of faradaic currents, and hence insert direct effects on sensitivity and detection limit of the electroanalytical techniques. Despite the widespread techniques introduced until now, the extraction of the net faradaic current from total current still remains a challenge. In this work, by using multivariate curve resolution-alternating least square (MCR-ALS) as a powerful curve resolution-based chemometrics method, a straightforward method has been introduced for resolving faradaic current from the two types of charging currents (step charging current and induced charging current) in single potential step and staircase cyclic voltammetric methods. By simultaneous analyses of the current data matrices for different electrochemical systems, the three sources of current were successfully identified and their contributions in the total signal were easily calculated. Also, in this manner, the cell time constant can be obtained easily. Contrary to the previously reported methods, the present method does not need any pre-determined mathematical method; particularly there is no need to know the cell time constant.     

Analytical Determination and Bio-Monitoring of Platinum Group Elements in Roadside Grass Using Microwave Assisted Digestion and Electrothermal Atomic Absorption Spectrometry

The analytical conditions that enable the determination of traffic related platinum group elements (PGEs) in roadside grass using microwave digestion and electrothermal atomic absorption spectrometry were evaluated as an alternative to the biomonitoring of traffic related PGEs and Pb levels in urban areas. To optimize the analytical conditions and account for matrix effects that could import error in the analysis, method optimization was based on matrix simulation through analyte recovery from spiked unpolluted samples against a matrix blank. A mixture of nitric and hydrofluoric acid under progressively increasing microwave irradiation was optimized to afford the quantitative extraction of platinum group elements from plant matrix. Due to the low levels of platinum group elements in real samples, preconcentration was accomplished using sample evaporation followed by dissolution in dilute nitric acid prior to deliverance to the atomic detector. Quantitation limits below 1 ng g^?1 for Pd and Rh and lower than 2 ng g^?1 for Pt, were accomplished, enabling the monitoring of platinum group elements bioaccumulation in roadside grass with satisfactory recoveries, as determined from the analysis of spiked samples. The results from method application in an annual monitoring survey of PGEs and Pb levels in urban flora and other roadside media are presented and discussed.     

Analytical speciation as a tool to assess arsenic behaviour in soils polluted by mining

A study is performed to evaluate the occurrence of arsenic in polluted soils using acidic extractions and liquid chromatography–hydride generation–atomic fluorescence spectrometry (LC–HG–AFS) for speciation analysis. Seven soil samples were collected in an abandoned area polluted by mining in the Eastern Pyrenees (Spain), and two uncontaminated soils were taken for reference purposes. Moreover, the total arsenic content is evaluated in two different sieved fractions in order to obtain information on the possible particle-size-dependent association of arsenic with soil components. Soil samples were extracted with both phosphoric and ascorbic acids and the stabilities of the extracted species were studied. The arsenic species were determined by LC–HG–AFS. In addition, the ability of soil grinding to effect species change is also assessed. Arsenite and arsenate were found in the polluted soils, but only arsenate was found in the unpolluted soils. The quality of the results was assessed through a mass balance calculation and by analysing two soil Certified Reference Materials. Valuable information regarding arsenic occurrence in the studied soils is obtained from the speciation results. The presence of arsenite in the extracts can be attributed to arsenopyrite residues, whereas the presence of arsenate indicates release from weathered material. Figure Abandoned mining polluted area in Eastern Pyrenees     

铂单晶（210）,（310）和（610）阶梯晶面在甲酸氧化中的电催化特性

通过比较甲酸在Pt(210)、Pt(310)、Pt(610)3个阶梯晶面和在Pt(110)、Pt(100)2个基础晶面上的电氧化特性,揭示了在甲酸氧化中阶梯晶面的电催化特性不仅与该面原子排列对称结构种类有关,还依赖于这些对称结构的有序范围及所处的环境。     

A review of heavy metal contaminations in urban soils, urban road dusts and agricultural soils from China

This paper reviews quite a few heavy metal contamination related studies in several cities from China over the past 10 years. The concentrations, sources, contamination levels, sample collection and analytical tools of heavy metals in urban soils, urban road dusts and agricultural soils were widely compared and discussed in this study. The results indicate that nearly all the concentrations of Cr, Ni, Cu, Pb, Zn, As, Hg and Cd are higher than their background values of soil in China. Among the cities, the contamination levels of the heavy metals vary in a large range. The geoaccumulation index shows that the contamination of Cr, Ni, Cu, Pb, Zn and Cd is widespread in urban soils and urban road dusts of the cities. Generally, the contamination levels of Cu, Pb, Zn and Cd are higher than that of Ni and Cr. Agricultural soils are also significantly influenced by Cd, Hg and Pb derived from anthropogenic activities. The integrated pollution index (IPI) indicates that the urban soils and urban road dusts of the developed cities and the industrial cities have higher contamination levels of the heavy metals. The comparison of the IPIs of heavy metals in urban soils and urban road dusts of Shanghai, Hangzhou, Guangzhou and Hongkong reveals that the contamination levels of the metals in urban road dusts are higher than that in urban soils in the cities. Moreover, the main sources of the metals in urban soils, urban road dusts and agricultural soils are also different.     

铂微粒修饰聚2，5－二甲氧基苯胺电极对甲醇的电催化作用

将以铂微粒修饰玻碳电极（ＧＣ）为基体的聚２，５－二甲氧基苯胺膜（ＰＤＭＡ）形成修饰电极（Ｐｔ／ＰＤＭＡ／ＧＣ）．循环伏安实验表明，Ｐｔ／ＰＤＭＡ／ＧＣ电极对甲醇氧化比分散于玻碳电极上的铂催化活性更大。讨论了ＰＤＭＡ膜厚度、铂微粒含量及甲醇浓度对催化活性的影响。这种电极在酸性甲醇溶液中具有良好的稳定性。     

A green and fast chromatographic method for determining organic compound mobility in soils

Soil leaching column chromatography (SLCC) employing totally aqueous mobile phases has been used for the estimation of retardation factors (R) of heterocyclic compounds and heteroatom-substituted aryl derivatives Aniline, Aniside, Cresol, Hydroquinone, p-Nitroaniline, Phenol, Phenylenediamine, Piridine, Sulfanilamide, Sulfathiazole, Sulfamethoxazole, Metolachlor and Toluene in soils with low fraction of organic carbon. Small columns (0.39 cm × 10 cm i.d.) were packed with soils of different compositions (alluvial sediment, coarse sand and standard Eurosoil4 mixed with quartz). The theory of linear chromatography was employed to correlate statistical peak moments to R. Rs estimated through SLCC were compared with those derived from water–organic carbon partitioning coefficient reported in the literature. The adsorption isotherm of Metolachlor was measured by frontal analysis on a small column packed with alluvial sediment. The approach proposed for measuring the adsorption isotherm requires small amounts of chemicals and soils and does not need fraction collection nor detector calibration. The information obtained by SLCC experiments was used to predict the elution of Metolachlor and Phenol on a large column (8.9 cm × 100 cm i.d.) packed with alluvial sediment. The method used in this work, not making use of any chemical solvents, respects the fundamental concepts of green chemistry.     

Simultaneous determination of Pt and Rh by catalytic adsorptive stripping voltammetry, using hexamethylene tetramine (HMTA) as complexing agent

Characteristics of the adsorption/electro-reduction of Pt/Rh hexamethylene tetramine (HMTA) complex on static mercury drop electrode surface were studied. Cyclic voltammetry was carried out to get the insight about the mechanistic behaviour of the catalytic current obtained in the voltammetric scan of Pt/Rh HMTA complex in acidic solution. Adsorptive stripping voltammetry using HMTA as the complexing agent was found to be highly sensitive method for the determination of Pt/Rh. Voltammetric measurements were carried out using hanging mercury drop electrode (HMDE) as the working electrode, a glassy carbon rod as the counter and an Ag/AgCl/KCl_saturated as the reference electrode. Various electrochemical parameters like deposition potential, deposition time, concentration of the ligand, supporting electrolyte etc. were optimized. The detection limit of Pt and Rh was found to be 4.38 pML⁻¹ and 2.80 pML⁻¹, respectively for the deposition time of 30 s. Simultaneous determination of Pt(II) and Rh(III) in water samples was possible. The method was found to be free from the commonly occurring interfering ions such as Cu(II), Cd(II), Zn(II), Pb(II), Cr(III), Cr(VI), Fe(III), Fe(II), Ni(II) and Co(II). Spike recovery tests for both Pt and Rh in tap water and sea water samples were also carried out. The method has been verified by analyzing certified reference material (WMG-1).     

Determination of sildenafil citrate (viagra) and its metabolite (UK-103,320) by square-wave and adsorptive stripping square-wave voltammetry. Total determination in biological samples

The voltammetric behaviour of Sildenafil citrate (SC) and its main metabolite UK-103,320 (UK) was studied by square wave techniques, leading to two methods for its total determination in biological samples (urine and human serum). The application of the square wave (SW), without the adsorptive accumulation, shows a maximum response at −0.950 V. The effect of experimental parameters that affect this determination are discussed. The stripping technique, proved to be more sensitive, yielding signals three times larger than those obtained by applying a square wave scan without the previous accumulation. Two calibration graphs to determine total SC and UK concentration were established. Calibration graph in urine sample was linear in the range 4.4×10⁻⁸ to 4.8×10⁻⁷ M by the stripping mode with an accumulation time of 10 s. In the same conditions but in serum sample regression line was linear in the range 3.4×10⁻⁸ to 9.7×10⁻⁷ M. The two proposed methods (SW and square-wave adsorptive stripping voltammetry (SWAdSV)) were applied to the total concentration analysis in eight different biological samples by the standard addition method with satisfactory results in the four different serum samples by the SW and in the four urines by SWAdSV.     

TiO2负载单金属镍（铂）催化剂在甲烷解离反应中抗积碳能力的理论研究

研究碳原子在TiO2(101)负载镍或铂原子上的吸附行为对于阐明积碳问题提供了一个热力学线索.广义梯度近似密度泛函理论的PBE计算结果表明,镍在TiO2表面最稳定构型的吸附能为347.16 kJ/mol,铂对应的最稳定构型的吸附能为315.9 kJ/mol,而且2种金属的最稳定构型均处于TiO2表面2个O2c原子之间的桥位.吸附金属原子后,TiO2的态密度图中各电子峰向低能量方向移动,体系趋于稳定.从态密度图可知,碳的p轨道与金属原子的d轨道发生叠加,说明碳原子与金属原子成键,从而使吸附后Ni或Pt与O原子之间的相互作用减弱.碳原子吸附在Ni/TiO2(101)和Pt/TiO2(101)表面的最佳吸附结构的吸附能分别为474.19和570.08 kJ/mol,说明TiO2负载铂催化剂在甲烷重整反应中抗积碳能力较强.