Optimization of chemical and instrumental parameters in hydride generation laser-induced breakdown spectrometry for the determination of arsenic,antimony, lead and germanium in aqueous samples

A laser induced breakdown spectrometry hyphenated with on-line continuous flow hydride generation sample introduction system, HG-LIBS, has been used for the determination of arsenic, antimony, lead and germanium in aqueous environments. Optimum chemical and instrumental parameters governing chemical hydride generation, laser plasma formation and detection were investigated for each element under argon and nitrogen atmosphere. Arsenic, antimony and germanium have presented strong enhancement in signal strength under argon atmosphere while lead has shown no sensitivity to ambient gas type. Detection limits of 1.1 mg L⁻¹, 1.0 mg L⁻¹, 1.3 mg L⁻¹ and 0.2 mg L⁻¹ were obtained for As, Sb, Pb and Ge, respectively. Up to 77 times enhancement in detection limit of Pb were obtained, compared to the result obtained from the direct analysis of liquids by LIBS. Applicability of the technique to real water samples was tested through spiking experiments and recoveries higher than 80% were obtained. Results demonstrate that, HG-LIBS approach is suitable for quantitative analysis of toxic elements and sufficiently fast for real time continuous monitoring in aqueous environments.     

The protective role of melatonin under heavy metal-induced stress in Melissa Officinalis L.

Heavy metals, due to their inability to degrade, pose a serious environmental and nutritional problem. The accumulation of essential and non-essential heavy metals in living organisms reduces normal growth and development, resulting in acute poisoning, disease and even death of organisms. Melatonin is a very important multifunctional molecule in protecting plants from oxidative stress due to its ability to directly neutralize reactive oxygen species (ROS). Also, melatonin has a chelating property, which may contribute in reducing metal-induced toxicity. In this paper, the protective role of melatonin in counteracting metal-induced free radical generation was highlighted. Using the HPLC-FLD technique melatonin was identified and quantified in the roots and leaves of lemon balm ( Melissa officinalis L.), grown under photoperiod conditions. Furthermore, the response of plants pre-treated with exogenous 0.1 mM melatonin to the increased zinc (Zn) and cadmium (Cd) concentrations was observed, with changes in mineral (Ca, Mg), physiological and antioxidant status of the plant during heavy metals stress. The obtained melatonin concentrations were the highest published for dry plants so far. Elevated Cd and Zn levels in soil caused alternation in biochemical and physiological parameters of lemon balm leaves and roots. However, melatonin pre-treatment increased plant tolerance to heavy metals stress. Increased Cd and Zn uptake and their translocation into the leaves were also improved, indicating the possible use of melatonin in phytoremediation.     

Thermodynamic and electron-transfer properties of copper(II/I) polyaminothiaether complexes

In electron-transfer reactions, the change in the oxidation states of the reactants is generally accompanied by structural changes, which influence the electron-transfer kinetics. Previous studies on the systems of Cu(II)/(I) complexes involving cyclic tetrathiaether ligands indicated that inversion of coordinated donor atoms is a major geometric change during the overall electron-transfer process. Complex formation and isomerization studies on complexes with the 1,4,8,11-tetraazacyclotetradecane ligand have demonstrated that a necessary condition for conformational change is deprotonation followed by inversion of coordinated N atoms. When one or more nitrogen donor atoms in a ligand are replaced with sulfur, there is a choice of N or S inversion. It has been hypothesized that donor atom inversion (N or S donors) is a major factor that can lead to conformationally limited electron-transfer kinetics of copper systems. In the current study, the thermodynamic properties, electron-transfer kinetics and conformational changes in copper(II)[1,4,8-trithia-11-azacyclotetradecane], copper(II)[1,8-dithia-4,11-diazacyclotetradecane] and copper(II)[1,11,-dithia-4,8-diazacyclotetradecane] were determined in order to determine the effect of inversion of coordinated N atoms on electron-transfer rates as a function of low concentrations of water in an aprotic solvent (acetonitrile). By using controlled amounts of water as a hydrogen ion acceptor, deprotonation of amine nitrogen and nitrogen donor inversion was followed by comparing self-exchange rate constants for reduction and oxidation of the copper complexes. Data on thermodynamic properties and electron-transfer kinetics are presented. Possible conformational changes and kinetic pathways for complexes with ligands having mixed N and S donor sets are presented.     

Development of a continuous flow hydride generation laser-induced breakdown spectroscopic system: Determination of tin in aqueous environments

The design, construction and optimization studies of a continuous flow hydride generation laser-induced breakdown spectroscopic system, HG-LIBS, for the determination of tin in aqueous environments is presented. Optimization of the Laser Induced Breakdown Spectroscopy (LIBS) signal with respect to carrier gas flow rate, analyte, acid (HCl) and reductant (NaBH₄) concentrations and flow rates was performed by using spectral emission intensity from the neutral Sn(I) line at 284.0 nm under atmospheric pressures. With flow rates of 5.0 mL/min for NaBH₄ and 2.5 mL/min for HCl, optimum NaBH₄ and HCl concentrations were determined as 2.0% (w/v) and 1.0% (v/v), respectively. The hydride generation efficiency of the system was tested for tin hydride, stannane (SnH₄), by inductively coupled plasma mass spectrometer (ICP-MS). It was found that higher than 99% of the analyte was released into the gaseous phase. Upon optimization, the minimum detectable Sn concentration was found as 0.3 mg/L in water samples. That corresponds to more than two orders of increase in sensitivity compared to methods that employ common sample introduction techniques in liquids analysis by LIBS. Over 90% recoveries were obtained from spiking experiments with river, tap and drinking water samples. Results illustrate potential use of the continuous flow HG-LIBS system for monitoring of Sn concentrations in aqueous environments.     

Determination of Arsenic by Hydride Generation—Laser-Induced Breakdown Spectroscopy: Characterization of Interelement Interferences

In this study, interelement interferences were evaluated for the determination of arsenic in aqueous samples through laser-induced breakdown spectroscopy (LIBS) hyphenated with a hydride generation sample introduction system. Optimum instrumental and chemical parameters were selected and variation in LIBS signal intensity was recorded for As solution in the presence of comparable concentrations of interfering elements. No significant change in the signal intensity of As(I) 228.8?nm line was observed in the presence of alkali/alkali earth metals; however, the presence of hydride-forming elements has shown a noticeable decrease in the line emission strength of arsenic. The least variation in arsenic signal was observed in the presence of Ge, the most volatile of all. However, the signal has decreased to a greater extent in the presence of Sn, Sb, and Pb. The presence of interfering elements on electron temperature and electron number density of arsenic plasma has also been studied. Plasma temperatures calculated using both As and Ar emission lines in the Boltzmann equation were similar, being around 5000?K. The McWhirter criterion for stationary and homogenous plasmas was utilized for the establishment of the local thermodynamic equilibrium under the plasma conditions studied. Applicability of the technique for multielemental analysis of water samples was tested through spiking experiments. Arsenic signal showed 26% decrease in the multielemental mixture solution. LIBS is among a few atomic spectroscopic techniques that facilitate rapid and simultaneous multielemental analysis without extensive sample preparation steps. However, the analytical performance of the technique still requires more serious efforts to compete with other conventional techniques for routine analysis of environmental samples.