Speciation of volatile antimony compounds in culture headspace gases of Cryptococcus humicolus using solid phase microextraction and gas chromatography–mass spectrometry

Direct analysis of the volatile antimony compounds stibine (SbH₃), monomethylantimony, dimethylantimony (Me₂Sb) and trimethylantimony (Me₃Sb) using solid phase microextraction (SPME) with polydimethylsiloxane fibres and gas chromatography–mass spectrometry (GC–MS) is described. The best analyte to background signal ratio was achieved using a 20 min extraction time. Antimony species were separated using a 3% phenylmethylsilicone capillary column operated at a column pressure of 70 kPa, a flow rate of 1.4 ml min^?1 and temperature ramping from 30 to 36 °C at 0.1 °C min^?1. Cryogenic focusing of desorbed species was required to achieve resolution of antimony species. The optimized SPME–GC–MS method was applied to the analysis of headspace gases from cultures of Cryptococcus humicolus incubated with inorganic antimony(III) and (V) substrates. The headspace gases from biphasic (aerobic–anaerobic) biomass‐concentrated culture incubations revealed the presence of SbH₃, Me₂Sb and Me₃Sb. Stibine was the major antimony species detected in cultures amended with inorganic antimony(V). Me₃Sb was the sole volatile antimony species detected when cultures were amended with antimony(III). Copyright © 2002 John Wiley & Sons, Ltd.     

Occurrence of Volatile Metal and Metalloid Species in Landfill and Sewage Gases

Abstract

Speciation of volatile metals and metalloids in the environment is extensively described in literature. In order to investigate unstable volatile organometallics, on-line coupling of GC with ICP-MS was used. Preliminary results for gases of sewage sludge fermentation at thermophilic and mesophilic conditions are compared with the metal and metalloid speciation in landfill gases. In each case 20 L gas were sampled by cryogenic trapping. The species were identified by element-specific detection either by retention time of standards or by calculation of the boiling point correlation. Characteristic of the separation is the linear correlation of boiling point (bp/°C) versus retention time (rt/min) (bp = 6.39?rt -109.2, r² = 0.9926). The amounts of total volatile elements are estimated by semi-quantification. Cd, Sn. Hg, Pb (sewage gas) and Se, Te, Hg, Pb (landfill gas) were determined in the range of ng m^?3 level; As, Sb, Te and Bi (sewage gas) and As, Sn, Sb and Bi (landfill gas) in the μg m^?3 level range.     

Essential methodological improvements in the oxygen isotope ratio analysis of N‐containing organic compounds

The quantitative conversion of organically bound oxygen into CO, a prerequisite for the ¹⁸O/¹⁶O analysis of organic compounds, is generally performed by high‐temperature conversion in the presence of carbon at ～1450°C. Since this high‐temperature procedure demands complicated and expensive equipment, a lower temperature method that could be utilized on standard elemental analyzers was evaluated. By substituting glassy carbon with carbon black, the conversion temperature could be reduced to 1170°C. However, regardless of the temperature, N‐containing compounds yielded incorrect results, despite quantitative conversion of the bound oxygen into CO. We believe that the problems were partially caused by interfering gases produced by a secondary decomposition of N‐ and C‐containing polymers formed during the decomposition of the analyte. In order to overcome the interference, we replaced the gas chromatographic (GC) separation of CO and N₂ by reversible CO adsorption, yielding the possibility of collecting and purifying the CO more efficiently. After CO collection, the interfering gases were vented by means of a specific stream diverter, thus preventing them from entering the trap and the mass spectrometer. Simultaneously, a make‐up He flow was used to purge the gas‐specific trap before the desorption of the CO and its subsequent mass spectrometric analysis. Furthermore, the formation of interfering gases was reduced by the use of polyethylene as an additive for analytes with a N:O ratio greater than 1. These methodological modifications to the thermal conversion of N‐containing analytes, depending on their structure or O:N ratio, led to satisfactory results and showed that it was possible to optimize the conditions for their individual oxygen isotope ratio analysis, even at 1170°C. With these methodological modifications, correct and precise δ¹⁸O results were obtained on N‐containing analytes even at 1170°C. Differences from the expected standard values were below ±1‰ with standard deviations of the analysis <0.2‰. Copyright © 2010 John Wiley & Sons, Ltd.     

Applicability of microwave induced plasma optical emission spectrometry (MIP-OES) for continuous monitoring of mercury in flue gases

The applicability of microwave-induced plasma optical emission spectrometry (MIP-OES) for continuous monitoring of the environmentally hazardous element mercury in flue gases has been studied. Microwave induced plasmas have been sustained using both a TM₀₁₀ cavity (Beenakker resonator) and a so-called Surfatron. The analytical figures of merit for mercury in argon and helium discharges with both types of low-power micro-wave discharges have been examined. To determine mercury in artificial stack gases non-mixed argon/nitrogen discharges have been tested using a tangential flow torch design which allows to introduce a metal-loaded nitrogen gas flow as external gas and argon as internal gas. The addition of main flue gas components such as water vapour (concentration <6 g/m³), oxygen (<4% v/v) and carbon dioxide (<15% v/v) decrease the mercury line intensities to a considerable extent. Trace gases (CO, HCl, SO₂, NO) in concentrations typical to waste incineration processes have been found to have no effect on the mercury and the argon line intensities. The detection limit of mercury in nitrogen is 8 g/m³ using the TM₀₁₀ MIP and 10 g/m³ using the Surfatron. As such low detection limits are below the emission limit values of present-day environmental legislation MIP-OES is useful for on-line monitoring of mercury.Dedicated to Professor Dr. Dieter Klockow on the occasion of his 60th birthday     

Possible interferences of mercury sulfur compounds with ethylated and methylated mercury species using HPLC-ICP-MS

The HPLC-ICP-MS coupling technique is able to separate and detect methyl, ethyl and inorganic mercury isotopes specifically. An identification of ethyl mercury(+) is not possible when the widely used sodium tetraethylborate derivatisation method in combination with GC-AFS/AAS or ICP-MS techniques is performed because it contains ethyl groups.An unidentified compound with the same retention time as ethyl mercury was found in the HPLC chromatograms of industrial sewage samples and humic-rich soils of microcosm experiments after applying water vapour distillation. We also observed such unidentified peaks in samples of heavily contaminated sites in Eastern Germany, separated by HPLC fractionation only. In the experiments described, different mercury sulfur adducts were synthesised and tested for their retention times in the HPLC-ICP-MS system. It was found that the compound CH₃–S–Hg⁺ showed the same retention time as the ethyl mercury standard. It is therefore possible that ethyl mercury detected in chromatography by comparison of the retention time could also be due to an adduct of a sulfur compound and a mercury species. CH₃–S–Hg⁺ should be tested in other chromatographic mercury speciation methods for this effect.This work can also be regarded as a contribution to the discussion of artificially occurring methyl mercury in sediments during sample preparation.     

Volatile metal and metalloid species in gases from municipal waste deposits

We have detected volatile species of silicon, vanadium, arsenic, bromine, tin, antimony, tellurium, iodine, mercury, lead and bismuth in gases released from domestic waste deposits, using inductively coupled argon plasma mass spectrometry (ICP MS). By concurrent aspiration of a multielement standard solution for calibration, the element concentrations in deposit gas are found to be in the range from 0.1 ng m^?3 to 10 μg m^?3 gas. The global amount of some metal species emitted by this process may be of the order of several tons per year. These results suggest a biogeochemical pathway for the transfer of metals into the atmosphere via volatile species. This process may have significant influence on atmospheric cycling of metals as well as on metal toxicity within ecosystems.     

Alkylation of ionic mercury to methylmercury and dimethylmercury by methylcobalamin: Simultaneous determination by purge-and-trap GC in line with FTIR

A new approach was used to determine the reaction products of methylcobalamin and ionic mercury: purge-and-trap gas chromatography in line with Fourier transform infrared spectroscopy (PT GC/FTIR). This technique simultaneously and specifically determines the spectrum of dimethylmercury (DMeHg) and methylmercury produced by the reaction. No interference from other known organic mercury species could be detected. The method is different from others because it does not require solvent extraction of the organomercurials from aqueous solution, but relies on immediate volatilization from the reaction vessel by addition of 100 μl of 10 mM NaBH₄. The sample was purged with nitrogen for 10 min. The volatile species of mercury were trapped in a column at ?120°C, injected into the gas chromatograph and detected by FTIR. The efficiency of DMeHg and MeHg formation depended on different parameters: pH, temperature, reaction time, and the methylcobalamin/ionic mercury ratio. The initial reaction product was MeHg which was further transformed to DMeHg. The first methylation rate was two times faster than the second. MeHg formed first, reaching a maximum at higher temperatures (28°C and 37°C) and later decreasing as DMeHg formed. At lower temperatures (20°C) the rate of MeHg formation was slower, being similar to the formation rate of DMeHg. Different species of inorganic mercury such as HgSO₄, Hg(NO₃)₂, Hg(SCN)₂, HgCl₂ and Hgl₂ were used to study differences in methylation by methylcobalamin under standard conditions of acidity, temperature and cofactor Hg(II) ratio.     

Effect of excitation states of nitrogen on the surface nitridation of iron and steel in d.c. glow discharge plasma

The plasma nitriding phenomena that occur on the surfaces of iron and steel were investigated. In particular, the correlation between the kinds of nitrogen radicals and the surface nitriding reaction was investigated using a glow‐discharge apparatus. To control the excitation of nitrogen radicals, noble gas mixtures were used for the plasma gas. The highly populated metastables of noble gases selectively produce excited nitrogen molecules (N₂*) or nitrogen molecule ions (N₂⁺). The optical emission spectra suggested that the formation of N₂*‐rich or N₂⁺‐rich plasma was successfully controlled by introducing different kinds of noble gases. Auger electron spectroscopy and XPS were used to characterize the depth profile of the elements and chemical species on the nitrided surface. The nitride layer formed by a N₂⁺‐rich plasma had a much higher nitrogen concentration than that by a N₂*‐rich plasma, likely due to the larger chemical activity of the N₂⁺ species as well as the N₂⁺ sputtering bombardment to the cathode surface. The strong reactivity of the N₂⁺ species was also confirmed from the chemical shift of N 1s spectra for iron nitrides. An iron nitride formed by the N₂⁺‐rich plasma has higher stoichiometric quantity of nitrogen than that formed by the N₂*‐rich plasma. Besides the effect of nitrogen radicals on surface nitridation, the contribution of the chromium in steel to the nitriding reaction was also examined. This chromium can promote a nitriding reaction at the surface, which results in an increase in the nitrogen concentration and the formation of nitride with high nitrogen coordination. Copyright © 2010 John Wiley & Sons, Ltd.     

Cross sections for quenching of Cd(3PJ) as determined by resonance radiation flash photolysis

Absolute quenching cross sections of several gases for the equilibrated set of excited states Cd(³P₀, ³P₁) have been determined at 280°C. The excited atoms were generated by 3261 Å resonance radiation flash photolysis of cadmium vapor in excess bath gas, and monitored by kinetic absorption spectroscopy. Cadmium monohydride and cadmium monofluoride have been detected in absorption as primary products in certain CD(³P₀, ³P₁) quenching reactions.     

High efficiency of Mn–Ce‐modified TiO2 catalysts for the low‐temperature oxidation of Hg0 under a reducing atmosphere

Manganese‐ and cerium oxide‐modified titania catalysts were prepared by the deposition precipitation for the removal of elemental mercury (Hg⁰) from simulated yellow phosphorus off‐gas at low temperature. In addition, these catalysts were characterized by X‐ray diffraction, Brunauer–Emmett–Teller measurements, X‐ray photoelectron spectroscopy and field‐emission scanning electron microscope to determine the surface morphology of the obtained compounds and explore their formation mechanism. The results revealed that a Mn–Ce loading and reaction temperature of 10% and 150 °C, respectively, as well as a Mn/Ce molar ratio of 2:1, led to an optimal efficiency for the oxidation of elemental mercury. Furthermore, the effects of flue gas components were investigated. The presence of O₂ clearly promoted the oxidation of Hg⁰. A CO atmosphere did not affect the Hg⁰ oxidation, when compared with N₂, whereas the presence of H₂S and water vapor inhibited the oxidation process. Furthermore, the X‐ray photoelectron spectroscopy spectra of Hg 4f revealed that the elemental mercury adsorbed by the catalyst is present as HgO. Finally, the Hg⁰ catalytic oxidation mechanism was discussed on the basis of the experimental results and characterization analysis.     

Monolayer Co3O4 Inverse Opals as Multifunctional Sensors for Volatile Organic Compounds

Monolayers of periodic porous Co₃O₄ inverse opal (IO) thin films for gas‐sensor applications were prepared by transferring cobalt‐solution‐dipped polystyrene (PS) monolayers onto sensor substrates and subsequent removal of the PS template by heat treatment. Monolayer Co₃O₄ IO thin films having periodic pores (d≈500 nm) showed a high response of 112.9 to 5 ppm C₂H₅OH at 200 °C with low cross‐responses to other interfering gases. Moreover, the selective detection of xylene and methyl benzenes (xylene+toluene) could be achieved simply by tuning the sensor temperature to 250 and 275 °C, respectively, so that multiple gases can be detected with a single chemiresistor. Unprecedentedly high ethanol response and temperature‐modulated control of selectivity with respect to ethanol, xylene, and methyl benzenes were attributed to the highly chemiresistive IO nanoarchitecture and to the tuned catalytic promotion of different gas‐sensing reactions, respectively. These well‐ordered porous nanostructures could have potential in the field of high‐performance gas sensors based on p‐type oxide semiconductors.     

Role of Ceria in the Design of Composite Materials for Elemental Mercury Removal

The necessity to drastically act against mercury pollution has been emphatically addressed by the United Nations. Coal‐fired power plants contribute a great deal to the anthropogenic emissions; therefore, numerous sorbents/catalysts have been developed to remove elemental mercury (Hg⁰) from flue gases. Among them, ceria (CeO₂) has attracted significant interest, due to its reversible Ce³⁺/Ce⁴⁺ redox pair, surface‐bound defects and acid‐base properties. The removal efficiency of Hg⁰ vapor depends among others, on the flue gas composition and temperature. CeO₂ can be incorporated into known materials in such a way that the abatement process can be effective at different operating conditions. Hence, the scope of this account is to discuss the role of CeO₂ as a promoter, active phase and support in the design of composite Hg⁰ sorbents/catalysts. The elucidation of each of these roles would allow the integration of CeO₂ advantageous characteristics to such degree, that tailor‐made environmental solution to complex issues can be provided within a broader application scope. Besides, it would offer invaluable input to theoretical calculations that could enable the materials screening and engineering at a low cost and with high accuracy.     

Simultaneous Element-Selective Detection of C,F, Cl,Br, and I by Capillary Gas Chromatography Coupled with Microplasma Mass Spectrometry

Simultaneous element-selective detection of the halogens and carbon was accomplished with capillary gas chromatography coupled with microplasma mass spectrometry. The microplasma ion source was a radio frequency plasma contained inside the last 4–5 cm of the 0.32 mm i.d. fused silica capillary column. The ion source was located inside the high vacuum housing of the MS, and only the GC carrier gas (2.3 mL min⁻¹ of helium) was used for plasma generation. Atomic ions were detected in the positive mode. Detection limits were in the low picogram area, and the selectivity to carbon ranged from 8×10² for fluorine to higher than 10⁴ for the other halogens. By introduction of both hydrogen and oxygen as reagent gases, peak tailing was avoided by suppression of analyte reactions with the silica walls of the ion source. Special attention was given to the fluorine-selective detection due to an interfering background species at m/z 19, assumed to be H₃O⁺ originating from the reagent gases. The background signal was minimized by careful control of the power level.     

Diamondoid Nanostructures as sp3‐Carbon‐Based Gas Sensors

Diamondoids, sp³‐hybridized nanometer‐sized diamond‐like hydrocarbons (nanodiamonds), difunctionalized with hydroxy and primary phosphine oxide groups, enable the assembly of the first sp³‐C‐based chemical sensors by vapor deposition. Both pristine nanodiamonds and palladium nanolayered composites can be used to detect toxic NO₂ and NH₃ gases. This carbon‐based gas sensor technology allows reversible NO₂ detection down to 50 ppb and NH₃ detection at 25–100 ppm concentration with fast response and recovery processes at 100 °C. Reversible gas adsorption and detection is compatible with 50 % humidity conditions. Semiconducting p‐type sensing properties are achieved from devices based on primary phosphine–diamantanol, in which high specific area (ca. 140 m² g^?1) and channel nanoporosity derive from H‐bonding.     

Removal of Elemental Mercury from Simulated Flue Gas by Combining Non-thermal Plasma with Calcium Oxide

Mercury emission from coal combustion has been the fourth biggest pollutant in China, following the dusts, SO₂ and NO_X. The technology of non-thermal plasma has been widely studied for oxidizing gaseous elemental mercury at low temperature. In this paper, a new method of combining non-thermal plasma with calcium oxide was proposed to remove elemental mercury from simulated flue gas. The effects of non-thermal plasma, input energy, combination mode of plasma and calcium oxide on Hg⁰ removal were investigated in a wire-cylinder non-thermal plasma reactor, whose energy was supplied by a high voltage alternating current power. The peak voltage and energy of the non-thermal plasma were measured by an oscilloscope and a high voltage probe (1000:1). The results showed that most of Hg⁰ was converted to oxidized mercury in simulated flue gas by non-thermal plasma treatment. The Hg⁰ removal efficiency of CaO was improved remarkably strengthened by the non-thermal plasma, which was closely related to input energy, and the maximum mercury removal efficiency was about 80 % at an optimal input energy. Through temperature-programmed decomposition and desorption and energy dispersive spectroscopy analysis, the majority of mercury species on CaO surface were Hg₂O and HgO₃ rather than HgO. Therefore, it can be concluded that O₃ plays an important role in Hg⁰ oxidation under the condition of non-thermal plasma.     

The Chromatographic Analysis of Reduced Sulfur Gases in Antarctic Waters Following Pre-Concentration onto Tenax

Abstract

A technique was developed using sparging and pre-concentration onto a Tenax trap at ambient temperature allowing field measurements to be made of reduced sulfur gases in Antarctic marine and glacial melt waters. Following thermal desorption, gases were determined by gas chromatography using a flame photometric detector. Detection limits in ng 1^?1 were: H₂S 50, OCS 8, SO₂ 160, CH₃SH 6, CH₃SCH₃ 20 and CS₂ 2. Storage of melt water samples for more than 24 hours resulted in concentration changes of the reduced sulfur gases present. While the Antarctic environment imposed limitations on the analytical method, an investigation of various pond and marine waters was undertaken.     

Experimental Study on Demercurization Performance of Wet Flue Gas Desulfurization System

The demercurization performance of wet flue gas desulfurization (WFGD) system was investigated by measuring mercury concentrations at the inlet and outlet of WFGD system with a QM201H mercury analyzer. The selected desulfurizer included NH₃·H₂O, NaOH, Na₂CO₃, Ca(OH)₂ and CaCO₃. The influences of adding oxidant and coagulant such as KMnO₄, Fenton reagent, K₂S₂O₈/CuSO₄ and Na₂S into desulfurization solutions were also studied. The results show that elemental mercury is the main component of gaseous mercury in coal‐fired flue gas, and the proportion of oxidized mercury is less than 36%. Oxidized mercury could be removed by WFGD system efficiently, and the removal efficiency could amount to 81.1%–92.6%. However, the concentration of elemental mercury slightly increased at the outlet of WFGD as a result of its insolubility and re‐emission. Therefore, the removal efficiency of gaseous mercury is only 13.3%–18.3%. The mercury removal efficiency of WFGD system increased with increasing the liquid‐gas ratio. In addition, adding KMnO₄, Fenton reagent, K₂S₂O₈/CuSO₄ and Na₂S into desulfurization solutions could increase the mercury removal efficiency obviously. Various additives have different effects, and Na₂S is demonstrated to be the most efficient, in which a mercury removal efficiency of 67.2% can be reached.     

Bis(N,N′‐dimethylimidazol‐2‐yl­idene)mercury chlorotriiodo­mercury dimethyl sulfoxide solvate

The double mercury salt [Hg(C₅H₈N₂)₂][HgClI₃]·C₂H₆OS was prepared and its structure characterized. The [Hg(C₅H₈N₂)₂]²⁺ cation lies about an inversion centre and the [HgClI₃]^2? anion lies on a mirror plane. Cations and anions are linked to form a one‐dimensional polymer by weak Hg?Cl interactions [Hg?Cl 3.3744 (3) Å]. The mercury–carbene bond distance [2.076 (7) Å] is typical of a dicationic mercury–carbene species.     

ESI‐MS studies of palladium (II) complexes with 1‐(p‐toluenesulfonyl)cytosine/cytosinato ligands

The mononuclear complex Pd(1‐TosC‐N3)₂Cl₂ (2) containing 1‐(p‐toluenesulfonyl)cytosine (1) as a ligand, as well as dinuclear complexes Pd₂(1‐TosC^?‐N3,N4)₄ (3) and Pd₂(1‐TosC^?‐N3,N4)₂DMSO₂Cl₂ (4) containing the ligand anion (1‐TosC^?), was mass analyzed by electrospray ionization ion trap MS/MS and high resolution MS. Complexes 3 and 4 were obtained by recrystallization of 2 from DMF and DMSO, respectively. The behavior of complex 2 in different solutions was monitored by electrospray ionization mass spectrometry (ESI‐MS). Under the applied ESI‐MS conditions, complex 2 in methanol reorganized itself dominantly as new complex 3 and the solvent did not coordinate the formed species. In H₂O/DMSO, CH₃CN/DMSO and CH₃OH/DMSO solutions, complex 2 formed several new species with solvent molecules involved in their structure, e.g. complex 4 was formed as the major product. The newly formed species were also examined by LC‐MS‐DAD, confirming the solvent induced reorganization and the solution instability of complex 2. Copyright © 2009 John Wiley & Sons, Ltd.