Oxidation Reaction between Periodate and Polyhydroxyl Compounds and Its Application to Chemiluminescence

The oxidation reaction between periodate and polyhydroxyl compounds was studied. A strong chemiluminescent (CL) emission was observed when the reaction took place in a strong alkaline solution without any special CL reagent. However, in acidic or neutral solution, it was hard to record the CL with our instrument. It was interesting to find that in the presence of carbonate the CL signal was enhanced significantly. When O(2) gas and N(2) gas were blown into the reagent solutions, both background and CL signals of the sample were enhanced by O(2) and decreased by N(2). The spectral distribution of the CL emission showed two main bands (λ = 436-446 and 471-478 nm). Based on the studies of the spectra of CL, fluorescence and UV-visible, a possible CL mechanism was proposed. In strongly alkaline solution, periodate reacts with the dissolved oxygen to produce superoxide radical ions. A microamount of singlet oxygen ((1)O(2)*) could be produced from the superoxide radicals. A part of the superoxide radicals acts on carbonates and/or bicarbonates leading to the generation of carbonate radicals. Recombination of carbonate radicals may generate excited triplet dimers of two CO(2) molecules ((CO(2))(2)*). Mixing of periodate with carbonate generated were very few (1)O(2)* and (CO(2))(2)*. These two emitters contribute to the CL background. The addition of polyhydroxyl compounds or H(2)O(2) caused enhancement of the CL signal. It may be due to the production of (1)O(2)* during the oxidized decomposition of the analytes in periodate solution. This reaction system has been established as a flow injection analysis for H(2)O(2), pyrogallol, and α-thioglycerol and their detection limits were 5 × 10(-)(9), 5 × 10(-)(9), and 1 × 10(-)(8) M, respectively. Considering the effective reaction ions, IO(4)(-), CO(3)(2)(-), and OH(-) could be immobilized on a strongly basic anion-exchange resin. A highly sensitive flow CL sensor for H(2)O(2), pyrogallol, and α-thioglycerol was also prepared.     

Ozone monitoring based on a biosensor concept utilizing a reagentless alcohol oxidase electrode

An electrochemical method based on the concept of a biosensor for the monitoring of ozone is described for first time. The proposed method includes two parts: a selective sorbent for ozone, that is, eugenol, and a formaldehyde amperometric biosensor mounted into a flow-through cell. Ozone adds rapidly to the double bond of the allyl group of eugenol, which has been immobilized onto a hydrophobic C-18 reactor and the so produced formaldehyde is collected into the working buffer solution (sampler) and pumped to the detector. A multimembrane assembly consisting of an alcohol oxidase-modified nylon membrane sandwiched between an outer polycarbonate and an inner cellulose acetate membrane was fitted onto a Pt electrode and the enzymatically produced H2O2 was monitored at +0.65 V (vs Ag/AgCl/KCl 3 M). Under optimum conditions, a linear calibration curve over the concentration range 3-200 microg x mL(-1) ozone was constructed. The detection limit (S/N = 3) was calculated at 1.1 microg x mL(-1) ozone. The proposed method is interference-free from other gases such as O2, Ar, N2, N2O, NOCl, SO2, NH3, and CO2, which were tested at concentrations >200-fold higher than that of 100 microg x mL(-1) ozone used for comparison. Besides selectivity, the method is easy to perform and reproducible; its applicability in synthetic gaseous samples is also demonstrated.     

Diode laser sensor for measurements of CO, CO(2), and CH(4) in combustion flows

A diode laser sensor has been applied to monitor CO, CO(2), and CH(4) in combustion gases with absorption spectroscopy and fast extraction-sampling techniques. Survey spectra of the CO 3nu band (R branch) and the 2nu(1) + 2nu(2)(0) + nu(3) CO(2) band (R branch) near 6350 cm(-1) and H(2)O lines from the nu(1) + 2nu(2) and 2nu(2) + nu(3) bands in the spectral region from 6345 to 6660 cm(-1) were recorded and compared with calculated spectra (from the HITRAN 96 database) to select optimum transitions for species detection. Species concentrations above a laminar, premixed, methane-air flame were determined from measured absorption in a fast-flow multipass absorption cell containing probe-sampled combustion gases; good agreement was found with calculated chemical equilibrium values.     

Degradation of sulfamonomethoxine with Fe3O4 magnetic nanoparticles as heterogeneous activator of persulfate

The photocatalytic HCrO(4)(-) reduction was investigated in air equilibrated solution using the spinel CuFe(2)O(4) nanoparticles as sensitizers. The oxide is p-type semi conductor, prepared from nitrates decomposition. The catalytic performance increases with decreasing pH and the concomitant oxidation of salicylic acid contributes significantly to the photoactivity through the charges separation of electron/hole pairs (C(7)H(6)O(3)+6 O(2)+4h(+)+3 H(2)O → 7 CO(2)+4 H(3)O(+)). Evidence has been given to show the advantages of the hetero-system CuFe(2)O(4)/CdS in the chromate reduction. CuFe(2)O(4) acts as electrons pump and the electron transfer to chromate is mediated via CdS hexagonal variety (greenockite). A reduction of 60% occurs and the process is well described by a pseudo first order kinetic with a half life of ～2.8h and a quantum yield of ～0.12% for an initial HCrO(4)(-) concentration of 3 × 10(-4)M. An improvement up to 72% is obtained when the reaction occurs in a stirred reactor and no cadmium was detected after 6h illumination. The results indicate a competitive effect with the water reduction. The hydrogen evolutions are found to be 0.236 and 0.960 cm(3)mn(-1)g(-1) in presence and in absence of HCrO(4)(-), respectively.     

Determination of H2O and CO2 concentrations in fluid inclusions in minerals using laser decrepitation and capacitance manometer analysis

Water and carbon dioxide concentrations within individual and selected groups of fluid inclusions in quartz were analyzed by using laser decrepitation and quantitative capacitance manometer determination. The useful limit of detection (calculated as ten times the typical background level) is about 5 x 10(-10) mol of H2O and 5 x 10(-11) mol of CO2; this H2O content translates into an aqueous fluid inclusion approximately 25 micrometers in diameter. CO2/H2O determinations for 38 samples (100 separate measurements) have a range of H2O amounts of 5.119 x 10(-9) to 1.261 x 10(-7) mol; CO2 amounts of 7.216 x 10(-10) to 1.488 x 10(-8) mol, and CO2/H2O mole ratios of 0.011 to 1.241. Replicate mole ratio determinations of CO2/H2O for three identical (?) clusters of inclusions in quartz have average mole ratios of 0.0305 +/- 0.0041 1 sigma. Our method offers much promise for analysis of individual fluid inclusions, is sensitive, is selective when the laser energy is not so great as to melt the mineral (laser pits approximately 50 micrometers in diameter), and permits rapid analysis (approximately 1 h per sample analysis).     

二维气相色谱法快速分析高纯锗烷中杂质

采用二维气相色谱技术与脉冲氦离子化检测器相结合,测定高纯锗烷中杂质,并探讨了不同阀事件时间程序对分析结果的影响.该方法实现了通过一次进样完成锗烷中微量氢、氧(氩)、氮、一氧化碳、二氧化碳和甲烷杂质分析,结果表明该方法的重复性和准确性好.     

Photodegradation of direct yellow-12 using UV/H2O2/Fe2+

A detailed investigation of photodegradation of direct yellow-12 (DY12) using UV/H(2)O(2)/Fe(2+) has been carried out in a photochemical reactor. Experiments studied degradation as a function of concentration, decolorization and reduction in chemical oxygen demand (COD). The effect of operating parameters, such as UV, pH, amount of Fenton's reagent (H(2)O(2) and FeSO(4)), and amount of DY12 dye has also been determined. It has been observed that simultaneous utilization of UV irradiation with Fenton's reagent increases the degradation rate of DY12 dye. The dye quickly losses its color and there is an appreciable decrease in COD value, indicating that the dissolved organic have been oxidized. The kinetics of degradation of the dye in dilute aqueous solutions follows pseudo-first order kinetics. Final products detected at the end of the reaction include NO(3)(-), NO(2)(-), N(2)O, NO(2), SO(2), CO(2) and CO. Results indicate that dye degradation is dependent upon pH, UV-intensity, concentration of Fenton's reagent and dye. Acidic pH has been found to be more suitable in comparison to neutral and alkaline. The optimum concentration of Fenton's reagent (H(2)O(2)/Fe(2+)) was found as 1500/500 mg l(-1) for 50 mg l(-1) DY12 dye in water at pH 4. The results indicate that the treatment of DY12 dye wastewater with UV/Fe(2+)/H(2)O(2) system is efficient.     

Ametryn degradation in the ultraviolet (UV) irradiation/hydrogen peroxide (H2O2) treatment

Ultraviolet (UV) irradiation (253.7nm) in the presence of hydrogen peroxide (H(2)O(2)) was used to decompose aqueous ametryn. The concentrations of ametryn were measured with time under various experiment conditions. The investigated factors included H(2)O(2) dosages, initial pH, initial ametryn concentrations, and a variety of inorganic anions. Results showed that ametryn degradation in UV/H(2)O(2) process was a pseudo-first-order reaction. Removal rates of ametryn were greatly affected by H(2)O(2) dosage and initial concentrations of ametryn, but appeared to be slightly influenced by initial pH. Furthermore, we investigated the effects of four anions (SO(4)(2-), Cl(-), HCO(3)(-), and CO(3)(2-)) on ametryn degradation by UV/H(2)O(2). The impact of SO(4)(2-) seemed to be insignificant; however, Cl(-), HCO(3)(-), and CO(3)(2-) considerably slowed down the degradation rate because they could strongly scavenge hydroxyl radicals (OH) produced during the UV/H(2)O(2) process. Finally, a preliminary cost analysis revealed that UV/H(2)O(2) process was more cost-effective than the UV alone in removal of ametryn from water.     

H(2)O(2)-generating peroxidase electrodes as reagentless cyanide sensors

Inexpensive, reagentless, and simple (single-electrode) cyanide biosensors are developed using a pyrolytic graphite (PG) electrode on which horseradish peroxidase (HRP) is adsorbed. The electrode is poised at -300 mV vs Ag/AgCl for 40 s to reduce dissolved O(2) to H(2)O(2) at the PG surface. The generated H(2)O(2) accumulates in the diffusion layer. The potential is then stepped to 0 mV, at which the accumulated H(2)O(2) is reduced, though the O(2) reduction does not proceed. Since the H(2)O(2) reduction is catalyzed by HRP, the transient cathodic current is inhibited by cyanide. Therefore, the transient current is a function of the cyanide concentration. A HRP/PG electrode with saturated HRP coverage is reliable, and it can determine 10(-)(5)-10(-)(3) M cyanide. On the other hand, the electrode with lower HRP coverage is less reliable, though it is so sensitive as to detect 2 × 10(-)(7) M cyanide because the system is under kinetic control.     

Control of H2S emission from swine manure using Na-nitrite and Na-molybdate

Biogenic production of hydrogen sulphide (H2S) in oil reservoirs (souring) has been shown to be controlled effectively using nitrite and molybdate salts. In the present work the effects of addition of nitrite and molybdate on reducing the emission of H2S from swine manure slurry was investigated in the laboratory and semi-pilot scale systems. Addition of 80 mM nitrite or 2 mM molybdate (final concentration in the manure slurry) to fresh manure in the laboratory scale closed systems (125 mL and 4 L) reduced the concentration of H2S in the headspace gas from 1500 microL L(-1) to 10 microL L(-1) which maintained during the remaining period of trials (40-60 days). With aged manure, similar results were achieved with a lower level of nitrite (10 mM). Simultaneous or sequential additions of nitrite and molybdate to fresh manure had similar effects. Contrary to the systems simulating biological conditions in oil reservoirs in which simultaneous addition of nitrite and molybdate has been reported to have a synergistic effect, no synergism was observed when nitrite and molybdate were added to the manure simultaneously. Experiments with fresh manure slurry in the semi-pilot scale systems (200 L) confirmed the effectiveness of this approach in which addition of 80 mM nitrite or 2 mM molybdate or a combination of 80 mM nitrite and 2 mM molybdate decreased the concentration of the H2S in the headspace gas from an initial value of 500 microL L(-1) to a low level in the range 2-25 microL L(-1) and maintained these low levels during the remaining period of trials (16 days). The concentration of ammonia (NH3) in the headspace gas of the treated systems was similar to that observed in the control system (untreated), indicating that the treatment did not have an effect on the level of present NH3. Although the addition of nitrite or molybdate reduced emissions of H2S from swine manure and the associated health and safety concerns, it had little impact on the intensity of odour in the headspace gas samples from the semi-pilot scale system.     

Synthesis of a novel layered double hydroxides [MgAl(4)(OH)(12)](Cl)(2)·2.4H(2)O and its anion-exchange properties

A novel layered double hydroxide of Mg and Al with composition [Mg(0.96)Al(4.00)(OH)(12)]Cl(1.86)(CO(3))(0.03)·2.4H(2)O, designated as MgAl(4)-Cl, was synthesized by mixing crystalline gibbsite (γ-Al(OH)(3)) and solid MgCl(2)·6H(2)O with subsequent hydrothermal treatment at 160 °C for 72h. The MgAl(4)-Cl exhibited a crystalline material of a layered structure, as evidenced from X-ray diffraction. Anion uptake experiments with the MgAl(4)-Cl showed that Cl(-) in the interlayer space can be exchanged with anions such as Br(-), H(2)PO(4)(-), CO(3)(2-) or dodecyl sulfate (DS(-)) from aqueous solutions with preservation of the layered structure. Uptake of NO(3)(-), BrO(3)(-) or SO(4)(2-) on the MgAl(4)-Cl showed different behavior; these anions can be exchanged within 1h maintaining the layered structure, but a release of Mg(2+) cations from the sample was observed with increased reaction time, resulting in collapse of the layered structure and formation of the gibbsite phase, as determined from chemical analyses and X-ray diffraction.     

Comparison of four advanced oxidation processes for the removal of naphthenic acids from model oil sands process water

Four advanced oxidation processes (UV/TiO(2), UV/IO(4)(-), UV/S(2)O(8)(2-), and UV/H(2)O(2)) were tested for their ability to mineralize naphthenic acids to inorganic carbon in a model oil sands process water containing high dissolved and suspended solids at pH values ranging from 8 to 12. A medium pressure mercury (Hg) lamp was used, and a Quartz immersion well surrounded the lamp. The treatment goal of 5mg/L naphthenic acids (3.4 mg/L total organic carbon (TOC)) was achieved under four conditions: UV/S(2)O(8)(2-) (20mM) at pH 8 and 10, and UV/H(2)O(2) (50mM) at pH 8 (all with the Quartz immersion well). Values of electrical energy required to meet the treatment goal were about equal for UV/S(2)O(8)(2-) (20mM) and UV/H(2)O(2) (50mM) at pH 8, but three to four times larger for treatment by UV/S(2)O(8)(2-) (20mM) at pH 10. The treatment goal was also achieved using UV/S(2)O(8)(2-) (20mM) at pH 10 when using a Vycor filter that transmits light primarily in the mid and near UV, suggesting that that treatment of naphthenic acids by UV/S(2)O(8)(2-) using low pressure Hg lamps may be feasible.     

An On-Line Technique for the Determination of the δ(18)O and δ(17)O of Gaseous and Dissolved Oxygen

Few studies have used the stable isotopic composition of O(2) as a tracer of gas transport or biogeochemical processes in environmental research. Here we demonstrate field sampling techniques for gaseous and dissolved O(2) and describe an analytical method for measuring δ(18)O and δ(17)O values of O(2) in air, soil gas, and water samples using continuous-flow isotope-ratio mass spectrometry (CF-IRMS). A Micromass CF-IRMS was altered to accommodate a sample gas injection port prior to a CO(2) and H(2)O trap and GC column. The GC column was a 1-m, 5-? molecular sieve column held at 35 °C. The resolved sample O(2) was introduced to the IRMS via an open split. δ(18)O and δ(17)O values were determined by measurement of O(2) isotopes at m/z 34/32 and 33/32 and comparison to a reference pulse of O(2). Repeated injections of atmospheric oxygen yielded a repeatability (±SD) of ±0.17‰ for δ(18)O and ±0.5‰ for δ(17)O. IRMS source linearity was excellent for O(2) over a sample size range of 60-400 μL. The smallest sample for routine δ(18)O and δ(17)O determinations was ～80 μL of O(2), with a sample analysis time of 180 s. Preliminary results from a riverine and soil gas study illustrate natural oxygen isotope fractionation processes.     

Methodology for detection of carbon monoxide in hot, humid media by telecommunication distributed feedback laser-based tunable diode laser absorption spectrometry

Detection of carbon monoxide (CO) in combustion gases by tunable diode laser spectrometry is often hampered by spectral interferences from H2O and CO2. A methodology for assessment of CO in hot, humid media using telecommunication distributed feedback lasers is presented. By addressing the R14 line at 6395.4 cm(-1), and by using a dual-species-fitting technique that incorporates the fitting of both a previously measured water background reference spectrum and a 2f-wavelength modulation lineshape function, percent-level concentrations of CO can be detected in media with tens of percent of water (c(H2O)≤40%) at T≤1000?°C with an accuracy of a few percent by the use of a single reference water spectrum for background correction.     

On-line multicomponent trace-gas analysis with a broadly tunable pulsed difference-frequency laser spectrometer

The design and application of a novel automated room-temperature laser spectrometer are reported. The compact instrument is based on difference-frequency generation in bulk LiNbO(3). The instrument employs a tunable cw external-cavity diode laser (795-825 nm) and a pulsed diode-pumped Nd:YAG laser (1064 nm). The generated mid-IR nanosecond pulses of 50-muW peak power and 6.5-kHz repetition rate, continuously tunable from 3.16 to 3.67 mum, are coupled into a 36-m multipass cell for spectroscopic studies. On-line measurements of methane are performed at concentrations between 200 ppb (parts in 10(9) by mole fraction) and approximately 1%, demonstrating a large dynamic range of 7 orders of magnitude. Furthermore computer-controlled multicomponent analysis of a mixture containing five trace gases and water vapor with an overall response time of 90 s at an averaging time of only approximately 30 s is reported. A minimum detectable absorption coefficient of 1.1 x 10(-7) cm(-1) has been achieved in an averaging time of 60 s, enabling detection limits in the ppb range for many important trace gases, such as CH(4), C(2)H(6), H(2)CO, NO(2), N(2)O, HCl, HBr, CO, and OCS.     

Kinetics of decolorization of an azo dye in UV alone and UV/H(2)O(2) processes

The decolorization of C.I. Acid Red 27 (AR27), a monoazo anionic dye, was studied in the ultraviolet radiation (UV) alone and UV plus hydrogen peroxide (UV/H(2)O(2)) processes. The experimental results indicated that the kinetics of both oxidation processes fit well by pseudo-first order kinetics. The reaction rate was sensitive to the operational parameters and increased with increasing H(2)O(2) concentration and light intensity. The reaction orders of H(2)O(2) concentration and light intensity in both processes were obtained with linear regression method. A regression model was developed for pseudo-first order rate constant (k(ap,UV/H(2)O(2))) as a function of the Cconcentration and UV light intensity. (k(ap,UV/H(2)O(2)))=(2 x 10(-4)I(0.75)(0) + k(3)I(1.38)(0)[H(2)O(2)](n)(0))phi(AR27). As a result of two opposing effects of H(2)O(2) concentration at low and high concentrations, n has a value of 0.49 and -0.39 and k(3) has a value of 3 x 10(-4) and 0.1 for the regions of 0 mg l(-1) < [H(2)O(2)](0) < 650 mg l(-1) and 650 mg l(-1) < [H(2)O(2)](0) < 1500 mg l(-1)1, respectively. PhiAR27 is the initial dye concentration correlation index for developing of model for different initial concentrations of AR27. This rate expression can be used for predicting k(ap,UV/H(2)O(2) at different conditions in UV alone and UV/H2O2 processes. The results show that UV alone cannot be an efficient method for decolorization of AR27 in comparison with UV/H(2)O(2) process, therefore the first term of the model can be neglected.     

Studies on the Condensation Pathway to and Properties of Diiron Azadithiolate Carbonyls

Reaction of Fe(2)(SH)(2)(CO)(6) and HCHO, which gives Fe(2)[(SCH(2))(2)NH](CO)(6) in the presence of NH(3), affords the possible intermediate Fe(2)(SCH(2)OH)(2)(CO)(6), which has been characterized crystallographically as its axial-equatorial isomer. Fe(2)(SCH(2)OH)(2)(CO)(6) was shown to react with ammonia and amines to give Fe(2)[(SCH(2))(2)NR](CO)(6) (R = H, alkyl). Related hemithioacetal intermediates were generated by treatment of Fe(2)(SH)(2)(CO)(6) with RC(O)C(O)R (R = H, Ph, 4-F-C(6)H(4)) to give cycloadducts. The benzil derivative Fe(2)[S(2)C(2)(OH)(2)Ph(2)](CO)(6), a C(2)-symmetric species, was also characterized crystallographically. The acylated azadithiolate Fe(2)[(SCH(2))(2)NAc](CO)(6) was prepared by reaction of Li(2)Fe(2)S(2)(CO)(6) with (ClCH(2))(2)NC(O)Me. DNMR experiments show that the free energies of activation for rotation of the amide bond are the same for Fe(2)[(SCH(2))(2)NAc](CO)(6) and Fe(2)[(SCH(2))(2)NAc](CO)(4)(PMe(3))(2), which implies that the ligands on the iron centers do not strongly affect the basicity of the nitrogen. As a control, we showed that the thioamide Fe(2)[(SCH(2))(2)NC(S)Me](CO)(6) does exhibit a significantly higher barrier to rotation, attributable to the increased double-bond character of the N-C(S) bond.     

Fourier transform infrared spectroscopic method for the quantitative trace analysis of transition-metal carbonyl-labeled bioligands.

A quantitative FT-IR spectroscopic method has been developed for the trace analysis in chlorinated organic solvents of transition-metal carbonyl-labeled bioligands. In order to illustrate the widespread analytical potential of the method, three derivatives of the female hormonal steroid 17 beta-estradiol, containing Cr(CO)3, Cp2Mo2(CO)4 (Cp = eta 5-C5H5), and Co2(CO)6 as labels, and the anticonvulsant drug phenobarbital, labeled with (eta 5-C5H4)Mn(CO)3, were examined. The cobalt carbonyl marker proved to be the best sulted for quantitative analysis purposes, and the minimum tracer quantity detectable for this particular marker (64 scans, 4-cm-1 resolution, 3.5 min) was optimized in CCl4 solution at about 300 fmol (or 0.3 pmol, 180 pg) by using an ultralow volume (23.0 microL), gold light-pipe IR solution cell and a liquid nitrogen cooled, InSb (indium antimonide) IR detector. The repeatability of this radically different analytical procedure over the concentration range 1.0 x 10(-6) to 5.0 x 10(-8) M was good (coefficient of variance less than or equal to 6%) and the method provides the basis for a new immunological test--carbonylmetalloimmunoassay (CMIA).     

Ni(2+) and H(2)PO(4)(-) uptake properties of compounds in the CaTiO(3)-CaFeO(2.5) system

A batch method was used to investigate the uptake of heavy metal cations and anions by the compounds in the CaTiO(3)-CaFeO(2.5) system, in which a series of oxygen vacancies was systematically introduced into a perovskite structure as the x-value of Ca(Fe(x)Ti(1-x))O(3-x/2) was increased. Samples of CaTiO(3), CaFe(0.1)Ti(0.9)O(2.95), CaFe(0.5)Ti(0.5)O(2.75), CaFe(0.67)Ti(0.33)O(2.67) and CaFeO(2.5) were prepared by solid mixing (SM), co-precipitation (CP) and gel evaporation (GE) methods. The resulting samples were calcined at temperatures between 400 and 1000 °C. The target crystalline phases differed according to the preparation method, but in most cases were formed at 700-800 °C. The Ni(2+) sorption isotherms of all the samples were fitted better by the Langmuir model than by the Freundlich model, while in the case of H(2)PO(4)(-) sorption isotherms, these were better fitted by the latter model. The uptake ability increased with increasing x value of the samples. The maximum values for the saturated sorption of Ni(2+) (Q(0)(Ni(2+)) = 2.83 mmol/g) and H(2)PO(4)(-) (K(F)(H(2)PO(4)(-)) = 2.95 mmol/g) were achieved for x = 1 (i.e. CaFeO(2.5)) sample.     

Intracavity CO laser photoacoustic trace gas detection: cyclic CH(4), H(2)O and CO(2) emission by cockroaches and scarab beetles

A liquid-nitrogen-cooled CO laser and an intracavity resonant photoacoustic cell are employed to monitor trace gases. The setup was designed to monitor trace gas emissions of biological samples on line. The arrangement offers the possibility to measure gases at the 10(9) by volume (ppbv) level (e.g., CH(4), H(2) O) and to detect rapid changes in trace gas emission. A detection limit of 1 ppbv for CH(4) in N(2) equivalent to a minimal detectable absorption of 3 × 10(-9) cm(-1) can be achieved. Because of the kinetic cooling effect we lowered the detection limit for CH(4) in air is decreased to 10 ppbv. We used the instrument in a first application to measure the CH(4) and H(2) O emission of individual cockroaches and scarab beetles. These emissions could be correlated with CO(2) emissions that were recorded simultaneously with an infrared gas analyzer. Characteristic breathing patterns of the insects could be observed; unexpectedly methane was also found to be released.