Determination of inlet transmission and conversion efficiencies for in situ measurements of the nocturnal nitrogen oxides, NO3, N2O5 and NO2, via pulsed cavity ring-down spectroscopy

Pulsed cavity ring-down spectroscopy is a highly sensitive method for direct absorption spectroscopy that has been applied to in situ detection of NO3, N2O5 and NO2 in the atmosphere from a variety of platforms, including ships, aircraft, and towers. In this paper, we report the development of schemes to significantly improve the accuracy of these measurements. This includes the following: (1) an overall improvement in the inlet transmission efficiencies (92 +/- 2% for NO3 and 97 +/- 1% for N2O5) achieved primarily through a reduction in the inlet residence time; and (2) the development of a calibration procedure that allows regular determination of these efficiencies in the field by addition of NO3 or N2O5 to the inlet from a portable source followed by conversion of NO3 to NO2. In addition, the dependence of the instrument's sensitivity and accuracy to a variety of conditions encountered in the field, including variations in relative humidity, aerosol loading, and VOC levels, was systematically investigated. The rate of degradation of N2O5 transmission efficiency on the inlet and filter system due to the accumulation of inorganic aerosol was determined, such that the frequency of filter changes required for accurate measurements could be defined. In the absence of aerosol, the presence of varying levels of relative humidity and reactive VOC were found to be unimportant factors in the instrument's performance. The 1 sigma accuracy of the NO3, N2O5, and NO2 measured with this instrument are -9/+12, -8/+11, +/- 6%, respectively, where the -/+ signs indicate that the actual value is low/high relative to the measurement. The largest contribution to the overall uncertainty is now due to the NO3 absorption cross section rather than the inlet transmission efficiency.     

Flow tube kinetics investigation of the mechanism of detection in the sulfur chemiluminescence detector

Rate constants and their temperature dependencies were measured for the chemiluminescent reaction of ozone with the flame and furnace effluents of two commercially available sulfur detectors, the Sulfur Chemiluminescence detector (registered trademark of Sievers Instruments, Inc.) and the Chemiluminescent Sulfur Detector (registered trademark of Antek Instruments, Inc.). The absolute rate constants and activation energies agreed within experimental error with the well-established values for the SO + O(3) reaction in all detector configurations. When ozone was present in the reaction zone, the reaction of the furnace effluent with NO(2) also was in good agreement with the rate constant for the SO + NO(2) reaction. However, when ozone was not present in the reaction zone, little or no reaction occurred with NO(2). These results imply that an unknown sulfur species, X, is formed in the combustion zone and/or transfer line of the instrument and converted to SO upon reaction with ozone in the chemiluminescence detection cell. Based on our experimental results and known reaction rate constants, we can eliminate S(2), S(2)O, SO(2), S(2)O(2), HS, HSO, HSO(2), HOSO(2), and H(2)S as X. We hypothesize that X is S(3) formed in the association reaction of S atoms with S(2) within the transfer line.     

A compact diode laser cavity ring-down spectrometer for atmospheric measurements of NO3 and N2O5 with automated zeroing and calibration

A compact rack-mounted cavity ring-down spectrometer (CRDS) for simultaneous measurements of the nocturnal nitrogen oxides NO(3) and N(2)O(5) in ambient air is described. The instrument uses a red diode laser to quantify mixing ratios of NO(3) (at its absorption maximum at 662 nm) and of N(2)O(5) following its thermal dissociation to NO(3) in a second detection channel. The spectrometer is equipped with an automated zeroing and calibration setup to determine effective NO(3) absorption cross-sections and NO(3) and N(2)O(5) inlet transmission efficiencies. The instrument response was calibrated using simultaneous measurements of NO(2), generated by thermal dissociation of N(2)O(5) and/or by titration of NO(3) with excess NO, using blue diode laser CRDS at 405 nm. When measuring ambient air, the (2σ, 10 s) precision of the red diode CRDS varied between 5 and 8 parts-per-trillion by volume (pptv), which sufficed to quantify N(2)O(5) concentrations under moderately polluted conditions. Sample N(2)O(5) measurements made on a rooftop on the University of Calgary campus in August 2010 are presented. A maximum N(2)O(5) mixing ratio of 130 pptv was observed, corresponding to a steady-state lifetime of less than 50 min. The NO(3) mixing ratios were below the detection limit, consistent with their predicted values based on equilibrium calculations. During the measurement period, the instrument response for N(2)O(5) was 70% of the theoretical maximum, rationalized by a slight mismatch of the laser diode output with the NO(3) absorption line and a N(2)O(5) inlet transmission efficiency less than unity. Advantages and limitations of the instrument's compact design are discussed.     

Dual-inlet chemical amplifier for atmospheric peroxy radical measurements

The state-of-the-art of peroxy radical measurements using the technique of chemical amplification has matured in recent years. The NCAR chemical amplifier has been improved over previous versions by employing a dual-inlet system that allows more rapid switching between measurement and background modes. Further improvement is realized by the use of two NO(2) detectors. The dual-inlet chemical amplifier (DICHAMP) employs two identical glass inlet reactor-NO(2) detector combinations, one of which is operated in the background, while the other operates in the radical measurement mode. This instrument is less sensitive to fluctuations in ambient ozone than the single-channel version because of the continuous monitoring of the background and background plus radical signals. The single-inlet, dual-inlet with single-detector, and DICHAMP instruments are compared through theoretical calculations of the effect of noise at a given frequency and amplitude on retrieved radical levels. Laboratory experiments were conducted to support the theoretical results. Ambient radical concentrations were determined using these configurations to evaluate the performance under actual measurement conditions.     

A kinetic method for HO2*/O2*- determination in advanced oxidation processes

A new kinetic method is developed for the determination of hydroperoxyl radical (HO(2)(*))/superoxide radical (O(2)(*)(-)) in aqueous solution, and the calibration using a kinetic half-life technique is also established for determining the concentration of HO(2)(*)/O(2)(*)(-) as produced in the UV/H(2)O(2) process. This new method is based on the reduction of Fe(3+)-EDTA into Fe(2+)-EDTA by HO(2)(*)/O(2)(*)(-) and the well-known Fenton-like reaction of H(2)O(2) and Fe(2+)-EDTA to yield the hydroxyl radicals (OH(*)). Benzoic acid scavenges the OH radicals to produce hydroxybenzoic acids, which are analyzed by fluorescence detection (lambda(ex) = 320 nm; lambda(em) = 400 nm). The limit of detection for the new method depends on the pH values, and it is determined as 3.22 x 10(-)(11) M with signal-to-noise ratio of 2 at pH 5. In addition, the present technique has the advantage of using inexpensive and easily available nonenzymatic reagents that do not require the specific instrument and chemicals and of being insensitive to the moderate concentration of possible interferences often found in aqueous phase.     

Trace detection of atmospheric NO2 by laser-induced fluorescence using a GaN diode laser and a diode-pumped YAG laser

We report on the development of a highly sensitive detection system for measuring atmospheric NO(2) by means of a laser-induced fluorescence (LIF) technique at 473 nm using a diode-pumped Nd:YAG laser. A GaN-based laser diode emitting at 410 nm is also used as an alternative fluorescence-excitation source. For laboratory calibrations, standard NO(2) gas is diluted with synthetic air and is introduced into a fluorescence-detection cell. The NO(2) LIF signal is detected by a photomultiplier tube and processed by a photon-counting method. The minimum detectable limits of the NO(2) instrument developed have been estimated to be 0.14 ppbv and 0.39 ppbv (parts per billion, 10(-9), by volume) in 60 s integration time (signal-to-noise ratio of 2) for 473 and 410 nm excitation systems, respectively. Practical performance of the instrument has been demonstrated by the 24 hour continuous measurements of ambient NO(2) in a suburban area.     

High-sensitivity instrument for measuring atmospheric NO2

We report on the development of a high-sensitivity detection system for measuring atmospheric NO2 using a laser-induced fluorescence (LIF) technique around 440 nm. A tunable broad-band optical parametric oscillator laser pumped by the third harmonic of a Nd:YAG laser is used as a fluorescence excitation source. The laser wavelength is tuned at peak and bottom wavelengths around 440 nm alternatively, and the difference signal at the two wavelengths is used to extract the NO2 concentration. This procedure can give a good selectivity for NO2 and avoid interferences of fluorescent or particulate species other than NO2 in the sample air. The NO2 instrument developed has a sensitivity of 30 pptv in 10 s and S/N = 2. The practical performance of the detection system is tested in the suburban area for 24 h. The intercomparisons between the LIF instrument and a photofragmentation chemiluminescence (PF-CL) instrument have been performed under laboratory conditions. The correlation between the two instruments is measured up to 1000 pptv. A good linear relationship between the LIF measurements and the PF-CL measurements is obtained.     

Off-axis cavity ringdown spectroscopy: application to atmospheric nitrate radical detection

Atmospheric nitrate radicals (NO3) are detected using off-axis cavity ringdown spectroscopy (CRDS) for the first time to our knowledge with a room-temperature continuous-wave (cw) diode laser operating near 662 nm. A prototype instrument was constructed that achieved a 1sigma absorption sensitivity of 5 x 10(-10) cm(-1) Hz(-1/2), corresponding to a 1.4 part per trillion by volume 2sigma detection limit in 4.6 s at 80 degrees C. This sensitivity is a significant improvement over a recent implementation of off-axis cavity-enhanced absorption spectroscopy and comparable to that of the most advanced cw CRDS and pulsed CRDS applications for atmospheric detection of NO3. A comparison of measurements of ambient air in Fairbanks, Alaska, recorded with the off-axis CRDS instrument and a previously characterized conventional cw CRDS instrument showed good agreement (R2 = 0.97).     

Influence of ozone on traffic-related particulate matter on the generation of hydroxyl radicals through a heterogeneous synergistic effect

Epidemiologic studies suggest that ozone (O(3)) and airborne particulate matter (PM) can interact causing acute respiratory inflammation and other respiratory diseases. Recent studies investigated the hypothesis that the effects of air pollution caused by O(3) and PM are larger than the effect of these two pollutants individually. We investigated the hypothesis that ozone and traffic-related PM (PM(10) and PM(2.5), diesel and gasoline exhaust particles) interact synergistically to produce increasing amounts of highly reactive hydroxyl radicals (HO) in a heterogeneous aqueous mixture at physiological pH. Electron paramagnetic resonance (EPR) and spin trapping were used for the measurements. Results showed that HO radicals are generated by the catalytic action of PM surface area with ozone and that EPR peak intensities are two to three times higher compared to PM samples without ozone. Incubation of the nucleoside 2'-deoxyguanosine (dG) in aqueous mixtures of ozone and PM at pH 7.4 resulted in the hydroxylation at C(8) position of dG. The formation of 8-hydroxy-2'-deoxyguanosine (8-OHdG) showed a 2-2.5-fold increase over control (PM without O(3)). These results suggest that PM and O(3) act synergistically generating a sustained production of reactive HO radicals. Partitioning of O(3) into the particle phase depends on the concentration, hygroscopicity and particle size.     

Effects of sodium modification, different reductants and SO(2) on NO reduction by Rh/Al(2)O(3) catalysts at excess O(2) conditions

Although many catalysts of NO reduction have been developed, the presence of excess O(2) and SO(2) significantly inhibits their performance when they are used to treat the incineration flue gas. To solve such problem, this study prepared new Rh/Al(2)O(3) catalysts and investigated the effects of Na modification, SO(2) and different reductants. Experimental results indicated that the average removal efficiency of NO at such high O(2) concentrations exceeded 80% when the Rh/Al(2)O(3) catalysts were used. CO was a better reductant than C(3)H(6) and the best concentration ratio of reductant/NO was equal to 1. Adding Na to modify Rh/Al(2)O(3) catalysts significantly enhanced the removal efficiency of NO from 80 to 99% at 250-300 degrees C, especially at relative high SO(2) concentrations. Unfortunately, Rh-Na/Al(2)O(3) catalysts do not have long-time activities for NO reduction, possibly because of the formation of NaNO(3). Both Rh/Al(2)O(3) and Rh-Na/Al(2)O(3) catalysts have good performance for NO reduction, they can feasibly be used to reduce NO in the flue gas from waste incineration.     

Chemiluminescent reaction of fluorescent organic compounds with KHSO5 using cobalt(II) as catalyst and its first application to molecular imprinting

The decomposition of peroxomonosulfate (HSO5-) has been investigated by chemiluminescence (CL). A weak CL was observed during mixing the HSO5- solution with the Co2+ solution in unbuffered conditions. An appropriate amount of fluorescent organic compounds (FOCs), such as dansyl amino acids and pyrene, was added to the KHSO5/Co2+ solution, a strong CL was recorded. A possible CL mechanism, based on studies of the fluorescence, CL, and UV-visible spectra and comparison of Co3+ oxidation ability with the SO4.- radical ion, was discussed. The CL from HSO5-/Co2+ is the emission of singlet oxygen produced from the catalytic decomposition of HSO5-. It was suggested that the decomposition of HSO5- in aqueous solution with Co2+ proceeds via one-electron transfer to yield SO4.- radical ion. The FOC was attacked by SO4.- radical ion and oxidized to decompose into small molecules. During this proceeding, CL emission was given out. The present CL system has been developed as a flow injection analysis for FOCs. The detection limits (S/N = 3) were in the concentration range 10(-9)-10(-7) M for FOCs. Oxidation decomposition and CL emission of the analytes have been used in the molecular imprinting recognition. As an initial attempt, dansyl-L-phenylalanine was used as a template molecule and methacrylic acid and 2-vinylpyridine were used as functional monomers. The network copolymer imprinted with dansyl-L-phenylalanine exhibits an affinity for the template molecule. When the flowing streams of HSO5- and Co2+ solutions mixing through the molecularly imprinted polymer particles filled the flow cell, the template molecule, dansyl-L-phenylalanine reacted with the HSO5-/Co2+ solution and CL was emitted. The dansyl-L-phenylalanine was decomposed during the CL process, and the cavities of a defined shape and an arrangement of functional groups complementary to the template in the polymer were left for the next sample analysis.     

Simultaneous removal of SO2 and NO by wet scrubbing using aqueous chlorine dioxide solution

The present study attempts to generate chlorine dioxide (ClO(2)) gas continuously by chlorate-chloride process and to utilize it further to clean up SO(2) and NO(x) gases simultaneously from the flue gas in the lab-scale bubbling reactor. Experiments were carried out to examine the effect of various operating parameters like input SO(2) concentration, input NO concentration, pH of the reaction medium, and ClO(2) feeding rate on the SO(2) and NO(x) removal efficiencies at 45 degrees C. Complete oxidation of NO into NO(2) occurred on passing sufficient ClO(2) gas into the scrubbing solution. SO(2) removal efficiency of about 100% and NO(x) removal efficiency of 66-72% were achieved under optimized conditions. NO(x) removal efficiency decreased slightly with increasing pH and NO concentration. Input SO(2) concentration had marginal catalytic effect on NO(2) absorption. No improvement in the NO(x) removal efficiency was observed on passing excess of chlorine dioxide in the scrubbing solution.     

Quantification of nitryl chloride at part per trillion mixing ratios by thermal dissociation cavity ring-down spectroscopy

Nitryl chloride (ClNO(2)) is an important nocturnal nitrogen oxide reservoir species in the troposphere. Here, we report a novel method, thermal dissociation cavity ring-down spectroscopy (TD-CRDS), to quantify ClNO(2) mixing ratios with tens of parts-per-trillion by volume (pptv) sensitivity. The mixing ratios of ClNO(2) are determined by blue diode laser CRDS of NO(2), produced from quantitative thermal dissociation of ClNO(2) in an inlet heated to 450 °C, relative to NO(2) observed in an unheated reference channel. ClNO(2) was generated by passing Cl(2) gas over a slurry containing a 1:10 mixture of NaNO(2) and NaCl. The TD-CRDS response was evaluated using parallel measurements of ClNO(2) by chemical ionization mass spectrometry (CIMS) using I(-) as the reagent ion and NO(y) (= NO + NO(2) + HNO(3) + ΣRO(2)NO(2) + ΣRONO(2) + HONO + 2N(2)O(5) + ClNO(2) + ...) chemiluminescence (CL). The linear dynamic range extends from the detection limit of 20 pptv (1 σ, 1 min) to 30 parts-per-billion by volume (ppbv), the highest mixing ratio tested. The ClNO(2) TD profile overlaps with those of alkyl nitrates, which has implications for nocturnal measurements of total alkyl nitrate (ΣAN = ΣRONO(2)) abundances by thermal dissociation (with detection as NO(2)) in ambient air.     

Analysis of pollutant chemistry in combustion by in situ pulsed photoacoustic laser diagnostics

A technique for gas analysis based on pulsed-laser-induced photoacoustic spectroscopy in the UV and the visible is presented. The laser-based technique and the associated analysis probe have been developed for the analysis of pollutant chemistry in fluidized beds and other combustion environments with limited or no optical access. The photoacoustic-absorption spectrum of the analyzed gas is measured in a test cell located at the end of a tubular probe. This test cell is subject to the prevailing temperature and pressure in the combustion process. The instrument response has been calibrated for N(2)O, NO, NO(2), NH(3), SO(2), and H(2)S at atmospheric pressure between 20 and 910 °C. The response of the probe was found to increase with pressure for N(2)O, NO, NH(3), and NO(2) up to 1.2 MPa pressure. The method and the probe have been used for detection and ranging of gas concentrations in a premixed methane flame. Some preliminary tests in a large 12-MW circulating bed boiler have also been done.     

Airborne laser infrared absorption spectrometer (ALIAS-II) for in situ atmospheric measurements of N2O, CH4, CO, HCl, and NO2 from balloon or remotely piloted aircraft platforms

The Airborne Laser Infrared Absorption Spectrometer II (ALIAS-II) is a lightweight, high-resolution (0.0003-cm(-1)), scanning, mid-infrared absorption spectrometer based on cooled (80 K) lead-salt tunable diode laser sources. It is designed to make in situ measurements in the lower and middle stratosphere on either a balloon platform or high-altitude remotely piloted aircraft. Chemical species that can be measured precisely include long-lived tracers N(2)O and CH(4), the shorter-lived tracer CO, and chemically active species HCl and NO(2). Advances in electronic instrumentation developed for ALIAS-I, with the experience of more than 250 flights on board NASA's ER-2 aircraft, have been implemented in ALIAS-II. The two-channel spectrometer features an open cradle, multipass absorption cell to ensure minimal contamination from inlet and surfaces. Time resolution of the instrument is 相似文献   

Assessment of the Effective Antioxidant Activity of Edible Films Taking into Account Films–Food Simulants and Films–Environment Interactions

Six gelatin films incorporating different ratios of sage oil (SO) and hemp oil (HO) were subjected to contact with food simulants and environmental exposure, respectively, for 3 months, at 15 000 lx light intensity, 40°C and 65% relative humidity. The migration and degradation, respectively, of the antioxidants into the simulants as well as their loss in the environment were mathematically modelled. The fastest release rate of antioxidants was noticed in the case of SO : HO 0 : 2 in 85% ethanol while the highest degradation rates were achieved after 18 days in the case of SO : HO 0 : 2 in water and 3% acetic acid and after 22 days in 85% ethanol. The antioxidants from SO : HO 0 : 2 were lost to the largest extent (5.37%) while those from SO : HO 1 : 1 to the lowest extent (3.49%). SO : HO 1 : 1 was selected as the most efficient film, by optimizing the amount of antioxidants available solely for food protection with the longest stability in the simulants. From industrial point of view, the mathematical modelling of the previously mentioned processes allows for the selection of the most effective film from a group with comparable physical–chemical–microbiological properties. Copyright © 2016 John Wiley & Sons, Ltd.     

N-Bi2O2CO3/CdSe量子点光催化氧化NO及原位红外光谱研究

本实验成功制备了氮掺杂碳酸氧铋(N-Bi₂O₂CO₃, N-BOC)/硒化镉量子点(CdSe QDs)复合光催化剂, 并将其运用于光催化降解室内空气污染物一氧化氮(NO)。X射线衍射、透射电子显微镜和光电子能谱测试结果表明N-BOC光催化剂在保持原有纳米片结构和形貌的基础上成功负载了CdSe QDs。光催化氧化NO实验结果显示CdSe QDs的引入可显著提高N-BOC的NO去除率, 并且二次毒副产物NO₂生成率大幅度降低至1%, 表明复合光催化剂具有极强的毒副产物抑制特性。固体紫外漫反射吸收光谱和发光光谱测试表明CdSe QDs拓宽并提升了N-BOC的光响应范围和能力, 并有效抑制了光生电子-空穴的复合效率。通过原位漫反射傅里叶变换红外光谱技术(DRIFTS)分析, 发现在N-BOC/CdSe QDs光催化氧化NO反应过程中没有NO₂信号产生, 仅观测到NO₃ ^-相关信号。机理分析表明超氧自由基(O₂ ^-)和光生空穴(h ⁺)是体系中可能存在的活性物种, 实现了对NO到NO₃ ^-的彻底氧化。     

Luminol/H2O2 chemiluminescence detector for the analysis of nitric oxide in exhaled breath

A new instrument for the detection of nitric oxide has been developed and applied to the analysis of exhaled breath. The instrument is based on conversion of NO to NO2, using the oxidant chromium trioxide, followed by detection of chemiluminescence in the reaction of NO2 with an alkaline luminol/H2O2 solution. The presence of H2O2 is found to enhance the sensitivity of NO2 detection by a factor of approximately 20. A bundle of porous polypropylene hollow fiber membranes is used to bring the gaseous sample into contact with the luminol solution. Chemiluminescence occurring within the translucent hollow fibers is detected using a miniature photomultiplier tube. The limit of detection for NO is 0.3 ppbv for S/N = 3, and the 1/e response time is 2 s. A large interference resulting from the 4-6% CO2 concentration in exhaled breath is removed by use of an ascarite scrubber in the air stream. Breath measurements of NO were made using a sampling technique developed by Sensor Medics (Yorba Linda, CA) with simultaneous detection using the luminol/H2O2 and NO + O3 chemiluminescence techniques. The two instruments were found to be in excellent agreement. Nitric oxide levels were in the range 6.0-22.0 ppbv for healthy individuals and 40.0-80.0 ppbv for individuals with asthma or a respiratory infection. This new detector offers the advantages of compact size, low cost, and a simple configuration compared to NO detectors based on NO + O3 chemiluminescence.     

Comparison of adsorption equilibrium models for the study of CL-, NO3- and SO4(2-) removal from aqueous solutions by an anion exchange resin

The removal of chloride, nitrate and sulfate ions from aqueous solutions by a macroporous resin is studied through the ion exchange systems OH(-)/Cl(-), OH(-)/NO(3)(-), OH(-)/SO(4)(2-), and HCO(3)(-)/Cl(-), Cl(-)/NO(3)(-), Cl(-)/SO(4)(2-). They are investigated by means of Langmuir, Freundlich, Dubinin-Radushkevitch (D-R) and Dubinin-Astakhov (D-A) single-component adsorption isotherms. The sorption parameters and the fitting of the models are determined by nonlinear regression and discussed. The Langmuir model provides a fair estimation of the sorption capacity whatever the system under study, on the contrary to Freundlich and D-R models. The adsorption energies deduced from Dubinin and Langmuir isotherms are in good agreement, and the surface parameter of the D-A isotherm appears consistent. All models agree on the order of affinity OH(-)相似文献   

Association between long-term exposure to outdoor air pollution and mortality in China: a cohort study

No prior cohort studies exist in China examining the association of outdoor air pollution with mortality. We studied 70,947 middle-aged men and women in the China National Hypertension Survey and its follow-up study. Baseline data were obtained in 1991 using a standard protocol. The follow-up evaluation was conducted in 1999 and 2000. Annual average air pollution exposure between 1991 and 2000, including total suspended particle (TSP), sulfur dioxide (SO(2)) and nitrogen oxides (NO(x)), were estimated by linking fixed-site monitoring data with resident zip code. We examined the association of air pollution with mortality using proportional hazards regression model. We found significant associations between air pollution levels and mortality from cardiopulmonary diseases and from lung cancer. Each 10 μg/m(3) elevation of TSP, SO(2) and NO(x) was associated with a 0.9% (95%CI: 0.3%, 1.5%), 3.2% (95%CI: 2.3%, 4.0%), and 2.3% (95%CI: 0.6%, 4.1%) increased risk of cardiovascular mortality, respectively. We found significant effects of SO(2) on mortality after adjustment for TSP. Conclusively, ambient air pollution was associated with increased cardiopulmonary and lung cancer mortality in China. These data contribute to the scientific literature on long-term effects of air pollution for high exposure settings typical in developing countries.