Determination of Platinum in Plant Samples by Voltammetric Analysis

A voltammetric method using solid electrode of glassy carbon as a working electrode is describes for determination of platinum in grass samples taken from the vicinity of a motorway. Standard addition was used for quantitative analysis of Pt in 0.05 M H₂SO₄. The analyte concentration in plant tissues reached 19.1±1.6 ng g^?1 for leaves of samples collected from the least polluted areas, and up to 136±2 ng g^?1 for roots of sample taken from the area of heavy road‐traffic.     

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.     

Voltammetric Peak Area as Instrumental Datum. A Possibility to Improve the Determination at Ultratrace Level Concentration of Platinum Group Metals (PGMs) and Lead. Application to Particulate Matter

Peak area as instrumental datum for determining the concentration of metals in solution instead of peak height is proposed for analytical voltammetric determinations. In the case of species present at ultratrace concentration level or having low reversibility degree of the electrodic processes, the employment of peak area permits to achieve limits of detection lower even more of one order of magnitude. The present work shows the possibility of determining at ultratrace level concentration Pd(II), Pt(II), Rh(III) and Pb(II) by voltammetry in particulate matter; these species, linked to vehicle emissions, show to have, in the supporting electrolytes employed, a very high irreversibility degree of the electrodic processes.     

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.     

Synthesis and Photophysical Properties of Monometallic C^C* Platinum(II) Formamidinate Complexes using Sterically Demanding Ligands

A novel class of cyclometalated platinum(II) complexes—previously considered to be inaccessible—was synthesized by an improved synthetic route utilizing ligands predicted by density functional theory calculations. Based on a concise quantum chemical screening three model ligands with varying steric demand were chosen and a series of six photoluminescent C^C* cyclometalated platinum(II) formamidinate complexes was obtained. The least sterically demanding ligand led to a bimetallic complex in two isomeric forms, which could be separated and confirmed by the corresponding solid-state structures. Sterically more hindered amidinate ligands gave the monometallic complexes supporting the theoretical predictions. The monometallic complexes show a significant hypsochromic shift of the emission wavelength, explained by the loss of the metal-metal interactions. Depending on the cyclometalating ligand quantum yields up to 87 % with short decay times were found for this new class of phosphorescent green-blue to pure blue platinum(II) emitters.     

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%.     

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.     

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 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     

Distribution of heavy metals of agricultural soils of central Greece using the modified BCR sequential extraction method

The state of heavy metal (Cd, Cu, Ni, Zn, Pb, and Cr) pollution was studied, in 440 texturally different soil profiles in Thessaly, an intensely cultivated region in Central Greece. The study was carried out in 2004 and 2005 on 220 soil samples for each year. Soil samples were classified in three soil orders: Endisols, Alfisols, and Vertisols according to the Soil Taxonomy System. The pseudo-total concentrations of heavy metals were determined by the aqua regia procedure. Heavy metals were also determined after division into four fractions by sequential extraction with (a) acetic acid (exchangeable and specifically adsorbed metals), (b) a reducing agent (bound to Fe/Mn hydroxides), (c) an oxidizing agent (bound to soil organic matter), and (d) aqua regia (bound to mineral structures, residual). The concentrations of all the metals studied were higher in the topsoil (0–30?cm) and lower in the second soil layer (30–60?cm). Concentrations of 70–82% of Cd, 39–64% of Cu, 41–69% of Ni, 29–51% of Zn, 75–89% of Pb, and 52–87% of Cr were found in the first two fractions. Cd appeared to be the most mobile of the metals studied, while Cu and Zn were found in forms associated with soil organic matter. The chemical partitioning patterns of Pb and Cr indicated that these metals are largely associated with the Fe–Mn hydroxides, while Cr was also found in the residual fractions. Significant correlations between heavy metals fractions and soil physicochemical parameters were obtained and discussed.     

A throughput method using the quick easy cheap effective rugged safe method for the quantification of ibuprofen and its main metabolites in soils

Quick, easy, cheap, effective, rugged, and safe extraction is a modern sample preparation method that involves a number of steps with a low susceptibility to error. The efficiency of a laboratory can be improved not only through labor reduction and consumable savings but also through the use of high‐throughput methods and the reduction of wastes. In commercially available kits, different salts and buffers are mixed in anhydrous packages. The composition of these kits are optimized and fixed for particular applications by the suppliers. In this work three model compounds (ibuprofen and two of its main metabolites: hydroxyibuprofen and carboxyibuprofen) were chosen and the amount of each salt (magnesium sulfate, sodium chloride, sodium citrate, and disodium citrate sesquihydrate) in the quick, easy, cheap, effective, rugged, and safe content was optimized for three different soil samples (soils A, B, and C) with different organic carbon contents, using a 2⁴ factorial design. The optimized extraction procedure was applied to 12 soil samples; ranging from river sediments to agricultural soils. Based on the analysis 100 samples, a price reduction of 5.1‐ (soil B), 5.7‐ (Soil C), and 6.1‐fold (soil A) was achieved without compromising the performance of the method when compared to commercial kits.     

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.     

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.