Detoxification of mercury in the environment.

In this study, a "green chemistry" approach was developed as an option for remediation of toxic mercury in the environment. Twenty mercury compounds were treated with an environmentally friendly agent cyclodextrin to produce stable non-toxic mercury in soil and water. The binding efficiency was determined using high performance liquid chromatography with diode-array detection. The stability of the cyclodextrin mercury complexes toward environmental microorganisms in water was estimated under OECD guidelines using gas chromatography-mass spectrometry. The toxicity of the cyclodextrin mercury compounds to terrestrial organisms was investigated by use of internationally recognized toxicity methods using mercuric acetate as a model contaminant. Key process conditions, for example pH, temperature, and amount of detoxifying agent were investigated and found to have significant effects on the toxicity of mercury. It was found that organic and inorganic mercury pollutants could be mineralized in the environment with cyclodextrins. The bound mercury compounds resisted biodegradation and were found to be non-toxic to environmental microorganisms under laboratory conditions.

Determination of Cr3+, CrO42-, and Cr2O72- in environmental matrixes by high-performance liquid chromatography with diode-array detection (HPLC-DAD).

A high-performance liquid chromatographic method with diode array detection (HPLC-DAD), based on chelation with ammonium pyrrolidinedithiocarbamate (APDC), has been developed for the determination of chromium species. Determination of Cr3+, CrO42-, and Cr2O72- was performed for standards and synthetic environmental matrixes. This method is robust, rugged, and can be used for rapid routine determination of chromium species with high precision and reliability. Sample pretreatment is simple. The method is capable of discriminating not only between Cr(III) and Cr(VI) but also between the chemical forms of Cr(VI) - CrO42- and Cr2O72-. By analysis of numerous samples the method has been shown to be selective, sensitive, and free from matrix interference, which is crucial for the determination of chromium species in difficult-to-analyze environmental matrixes. This method has been validated by means of an interlaboratory study. Although different speciation techniques were used during this study, there was good agreement between results from the two laboratories. The method detection limits were 7 and 4 mg L(-1) for Cr3+ and Cr2O72-, respectively. Recoveries of the analytes from spiked samples were 98% and 100% for Cr3+ and Cr2O72-, respectively. Both were based on a 10-mL sample volume spiked with 0.4 mg L(-1) chromium.

Atomization efficiency of a Massmann-type graphite furnace.

The atomization efficiency of the Perkin-Elmer HGA-400 for the production and containment of atomic vapour has been determined for Al, Co, Au, Ni, Fe, Ag, Ga and Cu by a method developed under non-isothermal conditions. The method takes into account the residence time and the shape of the absorbance signal profile. It is based on the entire absorption signal profile rather than on any part of it. The uncertainty in the method arises from calculation of the rate constant of atom loss due to temperature gradient which has a pronounced effect on the "effective" length of the analysis path when the atomizer is operated under non-isothermal conditions. The average value of the atomization efficiency for the eight elements used for this study was found to be about 0.10.

Arrhenius plots for activation energy of atomization in graphite-furnace atomic-absorption spectrometry.

Activation energy plots drawn by use of various Arrhenius-type equations for atomization reactions in graphite-furnace atomic-absorption spectrometry (GFAAS) do not give reliable kinetic information about the atomization mechanism of the analyte element beyond a few data-points located near the very beginning of the absorbance signal profile. These plots are non-linear if they are drawn with data points near the maximum of the absorbance signal profile. This paper presents two Arrhenius-type equations which give linear plots over a long range of data-points, and hence reliable values for the activation energy. Also, a simple method is proposed for calculating the activation energy from the data-points anywhere from the initial appearance of the absorbance signal to its maximum. Activation energy values given by these two equations and by the method of calculation are compared with each other and with those given by the commonly used methods. The calculated activation energy values obtained can be used to verify those obtained experimentally. The three proposed methods also provide reliable kinetic information on atom-formation reactions in GFAAS. A mechanism for the atomization of copper, based on the experimentally determined activation energy and reaction order is proposed.

Mechanism of cobalt atomization from different atomizer surfaces in graphite-furnace atomic-absorption spectrometry.

The mechanism of cobalt atomization from different atomizer surfaces in graphite-furnace atomic-absorption spectrometry has been investigated. The atomizer surfaces were pyrolytically coated graphite, uncoated electrographite, and glassy carbon. The activation energy of the rate-determining step in the atomization of cobalt (taken as the nitrate in aqueous solution) in a commercial graphite furnace has been determined from a plot of log k(s) vs. 1/T (for T values greater than the appearance temperature), where k(s) is a first-order rate constant for atom release, and T is the absolute temperature. The activation energy E(a), can be correlated either with the dissociation energy of CoO(g) or with the heat of sublimation of Co(s), formed by carbon reduction of CoO(s), the latter being the product of the thermal decomposition of Co(NO(3))(2). The mechanism for Co atomization seems to be the same for the pyrolytically coated graphite and the uncoated electrographite surfaces, but different for the glassy carbon surface. The suggested mechanisms are consistent with the chemical reactivity of the three atomizer surfaces, and the physical and thermodynamic properties of cobalt and its chemical compounds in the temperature range involved in the charring and atomization cycle of the graphite furnace.