Multivariate optimization of an axially-viewed inductively coupled plasma multichannel-based emission spectrometer for the analysis of environmental samples

An experimental design procedure was applied to optimize the operating conditions of an axially-viewed inductively coupled plasma emission spectrometer instruments equipped with echelle optics with cross dispersion and charge transfer device. The multivariate effect of carrier gas flow rate and r.f. power on several analytical figures was investigated and discussed. Both ultrasonic and pneumatic nebulization were used. For the final choice of the optimum, different criteria were taken into account, mainly plasma robustness, instrumental precision, analyte and background net emission, detection limits and signal-to-background ratios. It was found that the use of moderate power (1100W) and mean carrier gas flow rate (0.75 L/min) allows to obtain sufficient plasma robustness, satisfactory precision, and excellent signal-to-background ratios and limits of detection, favorable for ultratrace element determinations in environmental matrices.     

Neue neutrale und kationische Mono‐Aziridin‐Komplexe des Typs [CpMn(CO)2Az], [CpCr(NO)2Az]+ und [(Ph3P)(CO)4ReAz]+ über CO‐, Hydrid‐ und Chlorid‐Abspaltungsreaktionen

Novel Neutral and Cationic Mono‐Aziridine Complexes of the Type [CpMn(CO)₂Az], [CpCr(NO)₂Az]⁺, and [(Ph₃P)(CO)₄ReAz]⁺ via CO‐, Hydride‐, and Chloride‐Elimination Reactions The monoaziridine complexes 1 — 5 are obtained by three differently induced substitution reactions. The photolytically induced CO substitution reaction of [CpMn(CO)₃] with 2, 2‐dimethylaziridine leads to the neutral N‐coordinate aziridine complex [Cp(CO)₂Mn{$\overline{N(H)CMe₂C}$ H₂}] ( 1 ). The protonation of [(Ph₃P)(CO)₄ReH] with CF₃SO₃H and consecutive treatment with 2, 2‐dimethylaziridine or 2‐ethylaziridine gives the salt‐like aziridine complexes [(Ph₃P)(CO)₄Re{$\overline{N(H)CMe₂C}$ H₂}](CF₃SO₃) ( 2 ) or [(Ph₃P)(CO)₄Re{ H₂}](CF₃SO₃) ( 3 ) by hydride elimination reactions. The like‐wise salt‐like complexes [Cp(NO)₂Cr{$\overline{N(H)CMe₂C}$ H₂}](BF₄) ( 4 ) and [Cp(NO)₂Cr{ H₂}](CF₃SO₃) ( 5 ) are synthesized from [CpCr(NO)₂Cl] by chloride elimination with AgX (X = BF₄, CF₃SO₃) in the presence of 2, 2‐dimethylaziridine or 2‐ethylaziridine, respectively. As a result of X‐ray structure analyses, the metal atoms are trigonal pyramidally ( 1, 4, 5 ) or octahedrally ( 2, 3 , cis‐position) configurated; the intact three‐membered rings coordinate through the distorted tetrahedrally configurated N atoms. All compounds 1‐5 are stable with respect to the directed thermal alkene elimination to give the corresponding nitrene complexes; the IR, ¹H‐ and ¹³C{¹H}‐NMR, and MS spectra are reported and discussed.     

Thermisches Verhalten von Caesiumchloroferraten(III) und Caesiumchloroferrat(III)-Hydraten. II. Die Rehydratation der Zersetzungsprodukte von Cs3[FeCl6] – Eine ramanspektroskopische Untersuchung unter definierter Wasserdampfatmosphäre [1]

The Thermal Behaviour of Caesiumchloroferrates(III) and Caesiumehloroferrate(III) Hydrates. II. The Rehydration of Decomposition Products of Cs₃[FeCl₆] — A Raman Spectroscopic Study under Definite Atmosphere of Water Vapour Cs₃[FeCl₆] formed by dehydration of Cs₃[FeCl₆] · H₂O at about 160°C does not change at normal atmosphere within 3 till 4 hours. Rehydration under the vapour pressure of the eliminated water yields the monohydrate in nearly the same time. In the same manner rehydration of the solid mixture of Cs[FeCl₄] and 2 CsCl formed by thermal decomposition of the metastable Cs₃[FeCl₆] (280°C) produces the intermediates Cs₃[Fe₂Cl₉] and Cs₂[Fe(H₂O)Cl₅] in mixtures with CsCl and, finally, Cs₃[FeCl₆] · H₂O. The formation of Cs₃[Fe₂Cl₉] from Cs[FeCl₄] and CsCl is accelerated by water. The reaction cycle has been studied using Raman and IR spectroscopy. The results will be discussed with respect to thermoanalytical data.     

A multi-technique surface study of the mercury(II) chalcogenide ion-selective electrode in saline media

X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS), rotating disc electrode-electrochemical impedance spectroscopy (RDE-EIS) and synchrotron radiation-grazing incidence X-ray diffraction (SR-GIXRD) have been used to study the response mechanism of the mercury(II) chalcogenide ion-selective electrode (ISE) in saline media. XPS and SIMS have shown that the chalcogenide surface is poisoned by silver chloride, or a mixture of silver halides, on continuous exposure to synthetic and real seawater. Significantly, the in-situ SR-GIXRD study demonstrated that electrode fouling in synthetic seawater is linked to the formation of poorly crystalline or amorphous silver chloride, and that the low level of free mercury(II) in a calibration buffer (i.e., 10(-14) M) is able to undergo metathesis with silver(II) sulfide in the membrane generating mercury(II) sulfide. Significantly, the results of this detailed surface study have shown that silver chloride fouling of the electrode is ameliorated in real seawater comprising natural organic ligands, and this has been attributed to the peptization of silver chloride by the surfactant-like nature of seawater ligands at pH 8. RDE-EIS aging studies have revealed that the chalcogenide membrane experiences a sluggish charge transfer reaction in seawater, and contrary to a previous report for a static electrode, the seawater matrix does not passivate the RDE. The results of this XPS, SIMS, RDE-EIS and SR-GIXRD study have elucidated the response mechanism of the mercury(II) ISE in saline media.     

Vilsmeier formylation of 5,10,15-triphenylcorrole: expected and unusual products

5,10,15-Triphenylcorrole (1) reacts with the Vilsmeier reagent (POCl(3)/DMF) to give the corresponding 3-formyl derivative 3 as the major product. The regioselectivity of the reaction was proven by X-ray crystallography and only traces of the 2-formyl isomer were observed. A more polar product is also observed and this compound becomes the major product when an excess of DMF is used for the preparation of the Vilsmeier reagent, while the formation of the 3-formyl isomer is almost completely suppressed. X-ray crystallography allowed us to identify this compound as the fully substituted N-ethane bridged derivative 4, formed from the attack of the Vilsmeier reagent at the inner core of the macrocycle. This compound is unique among porphyrinoid macrocycles, and further confirms the peculiarity of corrole chemistry.     

Determination of hydroxycarbamates in aqueous matrices by direct derivatization and GC-MS analysis in chemical ionization mode

A rapid and effective procedure, developed for the determination of polar compounds in water, has been applied to hydroxycarbamates. In few minutes, it is possible to perform a catalyzed derivatization of such compounds directly in the aqueous medium, using n-hexyl chloroformate. Extraction with n-hexane and injection into a benchtop GC-MS system are the only two further steps to complete the analysis. Chemical ionization proved to be more effective than electron impact to produce valuable mass spectra in terms of selectivity and sensitivity. Linear quantitative responses were demonstrated over a two-order-of-magnitude range. The minimum detectable concentration was 3 ppb for acetohydroxamic acid and 10 ppb for hydroxyurethane, obtained from Po river water samples spiked with the two hydroxycarbamate standards.     

Use of modified rice husks as a natural solid adsorbent of trace metals: characterisation and development of an on-line preconcentration system for cadmium and lead determination by FAAS

The use of rice husks as an alternative adsorbent in an on-line preconcentration system for Cd (II) and Pb (II) determination by flame atomic absorption spectrometry (FAAS) is described. The potential of rice husks as a natural adsorbent was evaluated as a material modified with 0.75 mol l⁻¹ NaOH solution and in the unmodified form. For this task, several techniques such as spectroscopy and thermogravimetry were used for elucidation of possible functional groups responsible for the uptake of Cd (II) and Pb (II). Furthermore, based on adsorption studies and adsorption isotherms applied to the Langmüir model, it was possible to verify that modified rice husks present a higher adsorption capacity for both metals. After establishing this material as a promising natural adsorbent, it was used for on-line preconcentration of Cd (II) and Pb (II) metals. The multivariate optimisation of chemical and flow variables was performed by using a full factorial design (2⁴) including the following factors: preconcentration time, preconcentration flow rate, concentration and volume of eluent. The optimum pH values used for on-line preconcentration were taken from prior univariate experiments. Under optimised conditions for Cd (II) determination (4 min of preconcentration at a 6 ml min⁻¹ preconcentration flow rate, in which comprises 24 ml of preconcentration volume, 200 μl elution volume and 1.0 mol l⁻¹ HNO₃ solution as eluent), the system achieved a detection limit of 1.14 μg l⁻¹ and an enrichment factor of 72.4. Similar conditions were used for Pb (II) determination (4 min of preconcentration, 6 ml min⁻¹ preconcentration flow rate, 300 μl elution volume and 1.0 mol l⁻¹ HNO₃ solution as eluent) from which a detection limit of 14.1 μg l⁻¹ and enrichment factor of 46.0 were achieved. Also, rice husks have been shown to be a homogeneous and stable adsorbent in which more than 100 preconcentration/elution cycles provide a relative standard deviation (RSD) of less than 6.0% on the analytical signal. The satisfactory accuracy of the method developed was obtained by using spiked water samples (mineral water and lake water) and spiked red wine samples. These values were confirmed by electrothermal atomic absorption spectrometry (ETAAS). The certified reference material [pig kidney (CRM 186)] and the reference material [beech leaves (CRM 100)] were also used.     

Charge transfer in the Cl-CO cluster induced by core ionization

Ab initio calculations of core-ionization spectra of the anion-molecule Cl-CO cluster are performed. Particular attention is paid to the investigation of charge-transfer screening processes accompanying core ionization of the CO molecule in the cluster. The charge-transfer processes are very efficient and favored by the presence of a low-lying unoccupied pi* orbital in CO capable of accepting an electron from Cl-. The O1s(-1) and C1s(-1) core-ionization spectra are calculated and compared. Both reveal a breakdown of the quasiparticle picture of core ionization caused by the charge-transfer processes. Remarkable differences between these two spectra are found which manifest themselves in distinct intensity distributions in the prominent low-energy spectral bands. The underlying reason for these differences is elucidated and linked with the preference of the pi* orbital to localize mainly on carbon. Core-ionization spectra of anion-molecule clusters are very sensitive to the type of the molecule involved as the comparative analysis of the O1s(-1) core-ionization spectra of the Cl-CO and Cl-H(2)O clusters show.     

Trends in Preconcentration Procedures for Metal Determination Using Atomic Spectrometry Techniques

 Methods for metal preconcentration are often described in the literature. However, purposes are often different, depending on whether the methods are applied in environmental, clinical or technological fields. The respective method needs to be efficient, give high sensitivity, and ideally also is selective which is useful when used in combination with atomic spectroscopy. This review presents the actual tendencies in metal preconcentration using techniques such as Flame Atomic Absorption Spectrometry (FAAS), Electrothermal Atomic Absorption Spectrometry (ETAAS), Hydride Generation Atomic Absorption Spectrometry (HGAAS), Inductively Coupled Plasma Optical Emission Spectrometry (ICP OES) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Procedures based on related to electrochemical, coprecipitation/precipitation, liquid–liquid and solid–liquid extraction and atom trapping mechanisms are presented. Correspondence: Department of Analytical Chemistry, Universidade Estadual de Campinas – UNICAMP, P.O. Box 6154, 13083-970 Campinas, Brazil. e-mail: zezzi@iqm.unicamp.br Received December 20, 2001; accepted October 11, 2002