Reflection-grating self-pumped phase conjugation with optical feedback free of input conditions

A reflection-grating self-pumped phase-conjugate mirror is demonstrated with a photorefractive KNbO(3) crystal in a novel ring configuration. The feedback beam in the ring configuration is made to track the input probe beam automatically so that the phase conjugation is sustained without readjustment of the optical feedback loop when the angle or the position of the input probe beam is changed. The tracking feedback is realized by means of a simple three-lens erect imaging system. The angular and the positional acceptances for a tightly focused input beam of 50-μm diameter are Δθ(x). = 55 mrad, Δθ(y), = 67 mrad, and Δ(x) = 2.1 mm, Δ(y) = 4.2 mm, respectively.     

缺钾对水稻叶片叶绿素荧光参数的影响

以钾敏感型品种二九丰和钾迟钝型品种原丰早两种水稻为材料,研究了缺钾对水稻叶片叶绿素荧光参数的影响.结果表明,缺钾条件下,两品种水稻的初始荧光(Fo)、可变荧光与最大荧光比(Fv/Fm)以及非光化学猝灭系数(NPQ)与对照相比均无显著性差异;两品种水稻的光下可变荧光与最大荧光比(F′v/F′m)、光化学猝灭系数(qP)、实际光化学效率(ΦPSⅡ)以及光合电子传递速率(ETR)与对照相比均有所下降,其中二九丰的降幅更大.说明缺钾对各水稻品种叶绿素荧光参数的影响与其钾敏感性密切相关,F′v/F′m、qP、ΦPSⅡ和ETR四个叶绿素荧光参数可作为快速筛选耐缺钾水稻品种的参考指标.     

Automated measurement of nitrogen trifluoride in ambient air

We present an analytical method for the in situ measurement of atmospheric nitrogen trifluoride (NF(3)), an anthropogenic gas with a 100-year global warming potential of over 16,000. This potent greenhouse gas has a rising atmospheric abundance due to its emission from a growing number of manufacturing processes and an expanding end-use market. Here we present a modified version of the "Medusa" preconcentration gas chromatography/mass spectrometry (GC/MS) system of Miller, B. R.; Weiss, R. F.; Salameh, P. K.; Tanhua, T.; Greally, B. R.; Mühle, J.; Simmonds, P. G. Anal. Chem.2008, 80 (5), 1536-1545. By altering the techniques of gas separation and chromatography after initial preconcentration, we are now able to make atmospheric measurements of NF(3) with relative precision <2% (1σ) for current background clean air samples. Importantly, this method augments the currently operational Medusa system, so that the quality of data for species already being measured is not compromised and NF(3) is measured from the same preconcentrated sample. We present the first in situ measurements of NF(3) from La Jolla, California made 11 times daily, illustrating how global deployment of this technique within the AGAGE (Advanced Global Atmospheric Gases Experiment) network could facilitate estimation of global and regional NF(3) emissions over the coming years.     

Viscoelastic properties of low-viscosity liquids studied with thickness-shear mode resonators

The network analysis method was applied to AT cut quartz blanks (f(0) = 10 MHz), which were loaded with liquids of low and medium viscosity (water, methanol, ethanol, 1-propanol, 1-butanol, glycerol solutions). The shift of the resonance frequency Δf could be separated into a term due to rigidly coupled mass Δf(rig) and a term due to viscous damping Δf - Δf(rig). From the difference Δf - Δf(rig) and the broadening of the resonance curve, the complex shear modulus G = G' + iωη(L) was calculated. The viscosity coefficients η(L) are in good agreement with literature data. As G' > 0, it can be concluded that the examined fluids also reveal elasticity at shear frequencies in the MHz range. For the low-viscosity liquids, elastic contributions resulting from collective interactions of molecules are measurable but small and neglectable in most applications. The medium viscous liquid glycerol (98%) begins to exhibit considerable elasticity, resulting from the relaxation of separate molecules.     

Chemical constituents in particulate emissions from an integrated iron and steel facility

Particle emissions from four integrated iron and steel plant processes, i.e., coke making, sintering, cold forming, and hot forming, were investigated in this study. Particle compositions of 21 element species, 11 ionic species, elemental carbon (EC), organic carbon (OC) and 16 polyaromatic hydrocarbons (PAHs) were analyzed to create "fingerprints" of the particles emitted from various processes in an integrated iron and steel plant. Results indicated that element compositions (0.11-0.42 g/g), water-soluble ions (0.34-0.52 g/g), elemental carbon (0.008-0.14 g/g), organic carbon (0.02-0.06 g/g) and PAHs (0.52-6.2 mg/g) contributed to the particle mass. In general, sulfur had a higher mass contribution than the other elements, which resulted from the use of coal, flux, heavy oil, and many recycled materials in the iron and steel plant. The particle mass contribution of potassium and chlorine in the sinter plant was higher than in other processes; this may be attributed to the lower boiling point and volatility of potassium. In addition, many recycled materials were fed into the sinter plant, causing a high concentration of potassium and chlorine in the particle phase. Eight PAH compounds were analyzed in the four processes. The carcinogenic compound Benzo(a)pyrene (BaP) was detectable only in the sintering process.     

Analysis for voltammetric responses of molecular-solid tetrathionaphthalene confined on an electrode

The cyclic voltammetry (CV) of solid-state tetrathionaphthalene (TTN; particles with diameters from a few tens to hundreds of nanometers) confined on electrodes was analyzed quantitatively by considering the inert-zone potential, the thermodynamic and kinetic interactions, and the kinetics of the electrode reaction. Theoretical treatments are applied for clarifying the experimentally accessible corresponding parameters. From the potential of full peak width at half-height current (ΔE(p1/2)) and the peak current (i(p)) for the reversible CV voltammogram obtained at the slowest potential scan rate, the thermodynamic attraction forces in their active materials are evaluated as W = 3.67 ± 0.30 kJ mol(-1) for the (TTN)(0/1+) redox couple. From the shift of peak potential (ΔE(p)) and the changes in ΔE(p1/2) and/or the magnitude of i(p) for the irreversible CV obtained against the moderate potential scan rate, the value of the formal rate constant (k°') regarding surface electrode reaction of the (TTN)(0/1+) couple was evaluated as 0.59 ± 0.10 s(-1). The interaction parameters of W and ΔW[symbol: see text] being related to the thermodynamic and the kinetic interactions of the electrode reaction for the (TTN)(0/1+) couple were also evaluated as 3.39 ± 0.41 kJ mol(-1) and -1.39 ± 0.31 kJ mol(-1), respectively, from analysis for the irreversible CV.     

Formation of disinfection by-products in the chlorination of ammonia-containing effluents: significance of Cl2/N ratios and the DOM fractions

The presence of ammonia nitrogen (NH(3)-N) in the effluent strongly affected the formation of disinfection by-products (DBPs) during its chlorination. The effect of chlorine (as mg/L Cl(2)) to NH(3)-N (as mg/L N) mass ratios (Cl(2)/N) and the chemical fractions of dissolved organic matter (DOM) in the effluent on the DBPs formation was investigated. Results indicated that the formation of DBPs increased with increasing Cl(2)/N. The concentration and speciation of DBPs varied among different DOM fractions at different zones of chlorination breakpoint curves. The formation rate of total haloacetic acids (THAA) and total trihalomethanes (TTHM) was promoted after the chlorination breakpoint, whereas the reaction of monochloramine with HOCl to dichloramine may cause a decrease in the DBPs formation potential thereafter. Organic acids were found to be the dominant precursors of DBPs with or without the presence of NH(3)-N, which indicated that the CC, CO and C-O structures contributed to the formation of DBPs significantly. In addition, the incorporation of bromine in THMs of the HiA fraction increased with the increasing of Cl(2)/N mass ratios before the chlorination breakpoint, but decreased sharply after the breakpoint. ΔA(280) (absorbance at 280 nm), defined as A(280,initial)-A(280,final), was proved to be linearly related to the TTHM and THAA of wastewater without containing Br(-) during chlorination or chloramination.     

基于多岛遗传算法的橡胶浮置板弹性的优化

为研究橡胶弹性对橡胶浮置板轨道减振效果的影响,通过多岛遗传算法耦合Abaqus的自编程序,以《浮置板轨道技术规范(CJJ\T191-2012)》为依据,优化分析橡胶浮置板轨道的减振效果(优化变量为橡胶弹性),得出(1)橡胶浮置板轨道的橡胶弹性和减振效果指标不存在线性关系(即减小橡胶弹性,并不一定能得到最好的减振效果)。对于实际工程问题,建议通过优化方法,进行全局优化分析。(2)对于给出的橡胶弹性变化范围,当橡胶弹性模量取6.44×108N/m2时,橡胶浮置板轨道能够得到最好的减振效果。和现有某种橡胶浮置板轨道减振效果相比,优化后的橡胶浮置板轨道减振效果提升2.7 d B。     

Saturation of the ion-hammering effect for large non-hydrostatic capillarity stresses in colloidal silica nanoparticles

We investigate the role of capillarity stresses on the ion-hammering phenomenon when sub-micrometer colloidal particles are considered. To this end, nearly monodisperse, chemically synthesized silica (SiO?) colloids (100, 300 and 600 nm) were irradiated at room temperature (300 K) with 4 MeV Au ions for fluences up to Φ = 1.8 × 101? cm?2. It has been taken for granted that the transverse dimension of an ion-deformable amorphous material grows exponentially with the irradiation fluence, L(φ) = L?exp[A?Φ]. Here, we show that for sub-micrometer particles the irradiation-induced deformation saturates for larger fluences, L(φ)→const. The saturation fluence depends on the initial dimension of the colloidal nanoparticles: the smaller the dimension of the colloids, the lower the saturation fluence. Experimental data are successfully accounted for by having recourse to a phenomenological model first developed by Klaumünzer and further elaborated by van Dillen. We also estimate the evolution with fluence of the principal stresses inside the particles, σ??(φ) = σ??(φ) and σ??(φ), and we show that they evolve toward a steady-state value following a sigmoidal-like behavior. Furthermore, when stresses induced by the surface curvature become non-negligible the approximation often made that the deformation strain rate, A? = dL/L?dΦ, remains constant upon irradiation is no longer valid. We show that A? evolves with the irradiation fluence, e.g. A?→A(Φ), and we relate this behavior to the evolution of the stresses upon irradiation. Finally, this work allows us to define the limits of the ion-hammering effect when the non-hydrostatic capillarity stresses become important.     

All-solid-state flexible supercapacitors based on papers coated with carbon nanotubes and ionic-liquid-based gel electrolytes

All-solid-state flexible supercapacitors were fabricated using carbon nanotubes (CNTs), regular office papers, and ionic-liquid-based gel electrolytes. Flexible electrodes were made by coating CNTs on office papers by a drop-dry method. The gel electrolyte was prepared by mixing fumed silica nanopowders with ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][NTf(2)]). This supercapacitor showed high power and energy performance as a solid-state flexible supercapacitor. The specific capacitance of the CNT electrodes was 135 F g(-1) at a current density of 2 A g(-1), when considering the mass of active materials only. The maximum power and energy density of the supercapacitors were 164 kW kg(-1) and 41 Wh kg(-1), respectively. Interestingly, the solid-state supercapacitor with the gel electrolyte showed comparable performance to the supercapacitors with ionic-liquid electrolyte. Moreover, the supercapacitor showed excellent stability and flexibility. The CNT/paper- and gel-based supercapacitors may hold great potential for low-cost and high-performance flexible energy storage applications.     

THE EFFECTS OF CATHODIC POTENTIAL AND CALCAREOUS DEPOSITS ON CORROSION FATIGUE CRACK GROWTH RATE IN SEA WATER FOR TWO OFFSHORE STRUCTURAL STEELS

The effects of cathodic protection potential, corrosion products and stress ratio on corrosion fatigue crack growth rate have been studied on offshore structural steels. These materials were cathodically polarised in seawater and 3% sodium chloride solution at three potentials of -0.8, -1.0 and -1.1 V(SCE). The corrosion fatigue crack growth rate in seawater was greater than that in air and increased with more negative potentials. The maximum acceleration of crack growth rate in seawater was observed at the crack growth plateau which was independent of ΔK. Calcareous deposits precipitated within the cracks resulted in an increase of crack opening level and contributed to a reduction of the corrosion fatigue crack growth rate. Such a corrosion-product-wedging effect could be evaluated by using an effective stress intensity range, ΔK_eff. The estimation of corrosion fatigue crack growth rate in terms of ΔK_eff clarified the effect of hydrogen embrittlement under a cathodic potential. Thus the processes of cracking in seawater at cathodic potentials resulted from mechanical fatigue and hydrogen embrittlement with calcareous deposits reducing the crack growth rate. All these three mechanisms were mutually competitive.     

Single cell matrix-assisted laser desorption/ionization mass spectrometry imaging

Application of mass spectrometry imaging (MS imaging) analysis to single cells was so far restricted either by spatial resolution in the case of matrix-assisted laser desorption/ionization (MALDI) or by mass resolution/mass range in the case of secondary ion mass spectrometry (SIMS). In this study we demonstrate for the first time the combination of high spatial resolution (7 μm pixel), high mass accuracy (<3 ppm rms), and high mass resolution (R = 100?000 at m/z = 200) in the same MS imaging measurement of single cells. HeLa cells were grown directly on indium tin oxide (ITO) coated glass slides. A dedicated sample preparation protocol was developed including fixation with glutaraldehyde and matrix coating with a pneumatic spraying device. Mass spectrometry imaging measurements with 7 μm pixel size were performed with a high resolution atmospheric-pressure matrix-assisted laser desorption/ionization (AP-MALDI) imaging source attached to an Exactive Orbitrap mass spectrometer. Selected ion images were generated with a bin width of Δm/z = ±0.005. Selected ion images and optical fluorescence images of HeLa cells showed excellent correlation. Examples demonstrate that a lower mass resolution and a lower spatial resolution would result in a significant loss of information. High mass accuracy measurements of better than 3 ppm (root-mean-square) under imaging conditions provide confident identification of imaged compounds. Numerous compounds including small metabolites such as adenine, guanine, and cholesterol as well as different lipid classes such as phosphatidylcholine, sphingomyelin, diglycerides, and triglycerides were detected and identified based on a mass spectrum acquired from an individual spot of 7 μm in diameter. These measurements provide molecularly specific images of larger metabolites (phospholipids) in native single cells. The developed method can be used for a wide range of detailed investigations of metabolic changes in single cells.     

A visual study of R-404A/oil flow through adiabatic capillary tubes

The present study explores the potential of using visualization techniques to investigate refrigerant/oil flow through adiabatic capillary tubes. A literature review shows that these techniques have been used before for capillary tube investigations, but none of these studies focused on the refrigerant/oil phenomena. Therefore, the main objective is to investigate the flow of a refrigerant/oil mixture through a glass capillary tube, with special emphasis on the behavior of the vaporization point. The test fluids are R-404A (a near azeotropic blend) and a polyolester-type oil. Experimental data cover oil concentrations ranging from 5.6 to 6.9% (by mass), degrees of subcooling ranging from 6.2 to 21.5 °C (11.2 F to 38.7 F), and a condensing pressure of 1825 kPa (250 psig). The results show trends of mass flow rate, and give some useful insights about the location of the vaporization point for various oil concentrations and operating conditions.     

Extremely high-rate aqueous supercapacitor fabricated using doped carbon nanoflakes with large surface area and mesopores at near-commercial mass loading

Achieving a satisfactory energy-power combination in a supercapacitor that is based on all-carbon electrodes and operates in benign aqueous media instead of conventional organic electrolytes is a major challenge.For this purpose,we fabricated carbon nanoflakes (20-100 nm in thickness,5-μm in width) containing an unparalleled combination of a large surface area (3,000 m2·g-1 range) and mesoporosity (up to 72％).These huge-surface area functionalized carbons (HSAFCs) also had a substantial oxygen and nitrogen content (～10 wt.％ combined),with a significant fraction of redox-active carboxyl/phenol groups in an optimized specimen.Their unique structure and chemistry resulted from a tailored single-step carbonization-activation approach employing (2-benzimidazolyl) acetonitrile combined with potassium hydroxide (KOH).The HSAFCs exhibited specific capacitances of 474 F·g-1 at 0.5 A·g-1 and 285 F·g-1 at 100 A·g-1 (charging time ＜ 3 s) in an aqueous 2 M KOH solution.These values are among the highest reported,especially at high currents.When tested with a stable 1.8-V window in a 1 M Na2SO4 electrolyte,a symmetric supercapacitor device using the fabricated nanoflakes as electrodes yielded a normalized active mass of 24.4 Wh·kg-1 at 223 W·kg-1 and 7.3 Wh·kg-1 at 9,360 W·kg-1.The latter value corresponds to a charge time of ＜3 s.The cyclability of the devices was excellent,with 93％ capacitance retention after 10,000 cycles.All the electrochemical results were achieved by employing electrodes with near-commercial mass loadings of 8 mg·cm-2.     

Polychlorinated dibenzo-p-dioxins/dibenzofuran mass distribution in both start-up and normal condition in the whole municipal solid waste incinerator

Although many researches focused on the polychlorinated dibenzo-p-dioxins/dibenzofuran (PCDD/F) emissions from stack, in the bottom ash and in the surrounding environment, researches focused on PCDD/F mass distributions in the whole incineration plant have seldom been addressed. This study determined PCDD/F emissions in the whole plant. A high-resolution gas chromatograph/high-resolution mass spectrometer was utilized for analyzing 17 PCDD/F species. Experimental results displayed that PCDD/Fs were formed during fly ash from super heater (SH), economizer (EC), semi-dryer absorber (SDA) and fabric filter (FF) was transferred to fly ash pit. Mass distribution ratios of PCDD/Fs in g I-TEQ (Toxicity Equivalency Quantity) per week from stack, SH, EC, SDA, FF, generation and bottom residue (BR) in start-up operations were 14.6%, 0.1%, 8.3%, 1.0%, 41.7%, 33.4% and 0.9%, respectively. Above results indicated that main PCDD/F source in the MSWI was from fly ash. However, the fly ash is easily controlled and PCDD/F emitted from stack flue gases will be difficult to be handled. Therefore, we should pay more attention on PCDD/F emission from flue gases especially from start-up procedure. Besides, fly ash should be controlled by sodium hypophosphite before being landfilled. MSWI did require further detoxification treatments for the solid residues and flue gases.     

Polychlorinated dibenzo-p-dioxins/dibenzofurans distributions in ash from different units in a municipal solid waste incinerator

This study determined the polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) contents in ash in the super heater (SH), economizer (EC), semi-dryer absorber (SDA), fabric filter (FF), fly ash pit (FAP) and bottom residue (BR) in a municipal solid waste incinerator (MSWI). A high-resolution gas chromatograph/high-resolution mass spectrometer (HRGC/HRMS) was utilized for analyzing 17 PCDD/F species. Experimental results showed that average PCDD/F contents in ash samples from the SH, EC, SDA, FF, FAP and BR were 0.102, 0.788, 0.210, 1.95, 2.04 and 0.0218 ng I-TEQ g(-1), respectively. PCDD/F content was very low in the SH and BR due to high temperatures (around 461 degrees C in the SH and 914 degrees C in combustion chamber). Conversely, total PCDD/F content was significantly high in ash samples from the EC (around 340 degrees C), mainly because the temperature is within the favorable range of 250-400 degrees C for PCDD/F formation due to de nova reformation mechanisms. Although the SDA operated at 245 degrees C, the PCDD/F content decreased very significantly, mainly because the temperature was relatively low and because calcium carbonate was introduced into flue gases to dechlorinate and dilute chlorine-containing species. PCDD/Fs were captured by the active carbon in the FF. Furthermore, the duration that fly ash remained in the FF was longer than that for other incinerator units, and thus causing an increasing trend of PCDD/Fs level downstream (except the SDA). Total PCDD/Fs emission factors (microg tonnes-waste(-1); microg I-TEQ tonnes-waste(-1)) in ash samples from different units were: SH (42.3; 0.846), EC (326; 6.12), SDA (58.1; 1.10), FF (1540; 61.3), FAP (2950; 107) and BR (537; 4.31). Most PCDD/Fs in ash were contributed by the FF (about 56%), and the generation of PCDD/Fs in ash was significant (about 35%) during the transfer process from different units to the FAP. A strong and positive correlation in a logarithmic form existed between PCDD/Fs and chlorine (Cl(-1)) contents in ash. In Taiwan, the government policy for incineration residues advocates their reuse as road sub-bases or secondary building materials provided that total PCDD/Fs content is below the legal limit (1 ng I-TEQ g(-1)). Thus, ash with total PCDD/Fs content below the legal limit, such as that from the SH, EC, SDA and BR, can be collected and transferred to the FAP and reused. Ash with total PCDD/Fs content exceeding the legal limit, such as that from the FF, should be collected separately and be treated properly before being disposal in a landfill.     

Enhancement of acidic dye biosorption capacity on poly(ethylenimine) grafted anaerobic granular sludge

Developing a novel biosorbent with high capacity is crucial to remove dyes from waters in an efficient way. This study demonstrated that porous anaerobic granular sludge could be grafted with polyethylenimine (PEI), which definitely improved the sorption capacity towards Acid Red 18 (AR18) removal. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) study revealed that the PEI modification introduced a large number of amino groups on the surface of sludge, and the amino groups played an important role in the adsorption of dye molecule. Analysis of sorption data using a Boyd plot confirms the film diffusion was the rate-limiting step. The equilibrium data were well fitted Langmuir model, with a maximum AR18 uptake of 520.52 mg/g. Removal of AR18 decreased with the increasing pH and the maximum color removal was observed at pH 2.0. The sorption energy calculated from Dubinin-Radushkevich isotherm was found to be less than 8 for the biosorption of AR 18, which suggested that the biosorption processes of dye molecule onto modified anaerobic granules could be taken place by physical adsorption. Various thermodynamic parameters, such as ΔG(0), ΔH(0) and ΔS(0), were also calculated, which indicated that the present system was spontaneous and endothermic process.     

Biological/biomedical accelerator mass spectrometry targets. 1. optimizing the CO2 reduction step using zinc dust

Biological and biomedical applications of accelerator mass spectrometry (AMS) use isotope ratio mass spectrometry to quantify minute amounts of long-lived radioisotopes such as (14)C. AMS target preparation involves first the oxidation of carbon (in sample of interest) to CO 2 and second the reduction of CO 2 to filamentous, fluffy, fuzzy, or firm graphite-like substances that coat a -400-mesh spherical iron powder (-400MSIP) catalyst. Until now, the quality of AMS targets has been variable; consequently, they often failed to produce robust ion currents that are required for reliable, accurate, precise, and high-throughput AMS for biological/biomedical applications. Therefore, we described our optimized method for reduction of CO 2 to high-quality uniform AMS targets whose morphology we visualized using scanning electron microscope pictures. Key features of our optimized method were to reduce CO 2 (from a sample of interest that provided 1 mg of C) using 100 +/- 1.3 mg of Zn dust, 5 +/- 0.4 mg of -400MSIP, and a reduction temperature of 500 degrees C for 3 h. The thermodynamics of our optimized method were more favorable for production of graphite-coated iron powders (GCIP) than those of previous methods. All AMS targets from our optimized method were of 100% GCIP, the graphitization yield exceeded 90%, and delta (13)C was -17.9 +/- 0.3 per thousand. The GCIP reliably produced strong (12)C (-) currents and accurate and precise F m values. The observed F m value for oxalic acid II NIST SRM deviated from its accepted F m value of 1.3407 by only 0.0003 +/- 0.0027 (mean +/- SE, n = 32), limit of detection of (14)C was 0.04 amol, and limit of quantification was 0.07 amol, and a skilled analyst can prepare as many as 270 AMS targets per day. More information on the physical (hardness/color), morphological (SEMs), and structural (FT-IR, Raman, XRD spectra) characteristics of our AMS targets that determine accurate, precise, and high-hroughput AMS measurement are in the companion paper.     

Exact mass measurements on-line with high-performance liquid chromatography on a quadrupole mass spectrometer

Exact mass measurements were performed on-line with high-performance liquid chromatography on a quadrupole mass spectrometer. Compounds with molecular weights from 98 to 797, mainly aromatic sulfonates and sulfonamides, were analyzed with electrospray ionization in positive or negative mode. Internal mass calibration compounds were continuously added after separation. A Gaussian fit of the mass errors of 808 individual measurements (concentrations of 1-10 mg/L, 20-200 ng absolute on column) resulted in a mean error of 0.1 mmu (0.45 ppm) and a standard deviation sigma of 1.5 mmu (5.4 ppm). The 99.7% confidence intervals (3sigma) were +/-4.5 mmu (+/-16.2 ppm) for single mass measurements. Averaging 10 measurements further reduced the errors to less than +/-1.5 mmu (+/-5 ppm). Isobaric interferences with ions resulting from the mass calibrants were avoided by the use of complementary mass calibrants. The results were verified (differences below +/-4.5 mmu) with a LC/ oa-TOFMS. Limited mass range chromatograms were used to enhance selectivity in the analysis of mixtures. The method was applied to determine the elemental composition of a potential dye metabolite detected in anaerobically treated textile wastewater.     

Using electrospray-assisted laser desorption/ionization mass spectrometry to characterize organic compounds separated on thin-layer chromatography plates

Electrospray-assisted laser desorption/ionization (ELDI), an ionization method that combines laser desorption and electrospray ionization (ESI), can be used under ambient conditions to characterize organic compounds (including FD&C dyes, amines, extracts of a drug tablet) separated in the central track on a thin-layer chromatography (TLC) plate coated with either reversed-phase C18 particles or normal-phase silica gel. After drying, the TLC plate was placed on an acrylic sample holder set in front of the sampling skimmer of an ion trap mass analyzer. The chemicals at the center of the TLC plate were analyzed by pushing the sample holder into the path of a laser beam with a syringe pump. The molecules in the sample spot were desorbed by continuously irradiating the surface of the TLC plate with a pulsed nitrogen laser. Then, the desorbed sample molecules entered an ESI plume where they were ionized through the reactions with the charged species (including protons, hydronium ions and their cluster ions, solvent ions, and charged droplets) generated by electrospraying a methanol/water solution. MS/MS analyses were also performed to further characterize the analytes. The detection limit of TLC/ELDI/MS is approximately 10(-6) M. This was evaluated by using FD&C red dye as the standard. A linear relationship was found for the calibration curve with the concentration of FD&C red dye ranged from 10(-3) to 10(-6) M.