The gas-phase reactions of sulfuric acid catalyzed hydrolysis of formaldehyde and formaldehyde with sulfuric acid and H2SO4···H2O complex are investigated employing the high-level quantum chemical calculations with M06-2X and CCSD(T) theoretical methods and the conventional transition state theory (CTST) with Eckart tunneling correction. The calculated results show that the energy barrier of hydrolysis of formaldehyde in gas phase is lowered to 6.09 kcal/mol from 38.04 kcal/mol, when the sulfuric acid is acted as a catalyst at the CCSD(T)/aug-cc-pv(T+d)z//M06-2X/6-311++G(3df,3pd) level of theory. Furthermore, the rate constant of the sulfuric acid catalyzed hydrolysis of formaldehyde combined with the concentrations of the species in the atmosphere demonstrates that the gas-phase hydrolysis of formaldehyde of sulfuric acid catalyst is feasible and could be of great importance for the sink of formaldehyde, which is in previously forbidden hydrolysis reaction. However, it is shown that the gas-phase reactions of formaldehyde with sulfuric acid and H2SO4···H2O complex lead to the formation of H2C(OH)OSO3H, which is of minor importance in the atmosphere.
Despite the significant progress in the measurements of aerosol extinction and absorption using spectroscopy approaches such as cavity ring-down spectroscopy (CRDS) and photoacoustic spectroscopy (PAS), the widely used single-wavelength instruments may suffer from the interferences of gases absorption present in the real environment. A second instrument for simultaneous measurement of absorbing gases is required to characterize the effect of light extinction resulted from gases absorption. We present in this paper the development of a blue light-emitting diode (LED)-based incoherent broad-band cavity-enhanced spectroscopy (IBBCEAS) approach for broad-band measurements of wavelength-resolved aerosol extinction over the spectral range of 445-480 nm. This method also allows for simultaneous measurement of trace gases absorption present in the air sample using the same instrument. On the basis of the measured wavelength-dependent aerosol extinction cross section, the real part of the refractive index (RI) can be directly retrieved in a case where the RI does not vary strongly with the wavelength over the relevant spectral region. Laboratory-generated monodispersed aerosols, polystyrene latex spheres (PSL) and ammonium sulfate (AS), were employed for validation of the RI determination by IBBCEAS measurements. On the basis of a Mie scattering model, the real parts of the aerosol RI were retrieved from the measured wavelength-resolved extinction cross sections for both aerosol samples, which are in good agreement with the reported values. The developed IBBCEAS instrument was deployed for simultaneous measurements of aerosol extinction coefficient and NO(2) concentration in ambient air in a suburban site during two representative days.
Tunable diode laser absorption spectroscopy (TDLAS), as a noninvasive spectroscopic method, permits high-resolution, high-sensitivity, fast, in situ absorption measurements of atomic and molecular species and narrow spectral features in gaseous, solid, and liquid phases. Advances in new diode laser sources and laser spectroscopic techniques generally have triggered an increasing application of TDLAS in various disciplines (for example, atmospheric environmental monitoring, chemical analysis, industrial process control, medical diagnostics and combustion monitoring, etc.) over the last four decades. This article reviews some important developments in TDLAS, from its basic principles as a spectroscopic tool to the demonstration of gas absorption measurements, emphasizing signal enhancement and noise reduction techniques developed for improving current TDLAS performance.
This article describes the development and field application of a portable broadband cavity enhanced spectrometer (BBCES) operating in the spectral range of 440-480 nm for sensitive, real-time, in situ measurement of ambient glyoxal (CHOCHO) and nitrogen dioxide (NO). The instrument utilized a custom cage system in which the same SMA collimators were used in the transmitter and receiver units for coupling the LED light into the cavity and collecting the light transmitted through the cavity. This configuration realised a compact and stable optical system that could be easily aligned. The dimensions and mass of the optical layer were 676 × 74 × 86 mm and 4.5 kg, respectively. The cavity base length was about 42 cm. The mirror reflectivity at λ = 460 nm was determined to be 0.9998, giving an effective absorption pathlength of 2.26 km. The demonstrated measurement precisions (1σ) over 60 s were 28 and 50 pptv for CHOCHO and NO and the respective accuracies were 5% and 4%. By applying a Kalman adaptive filter to the retrieved concentrations, the measurement precisions of CHOCHO and NO were improved to 8 pptv and 40 pptv in 21 s.
Density of fine mode particles is an important physical parameter. However, its measurement and validation in the actual atmosphere are still difficult. In this study, the measurements at Shouxian, Anhui province, China (32.56°N, 116.78°E, elevation 22.7 m) in winter, are used for density retrieval and quality control. The effective density and number size distribution of fine mode aerosol can be obtained in real time, by using the scanning mobility particle sizer and aerodynamic particle sizer. During the experiment, the average density is about 1.66 ± 0.15 g/cm 3 with the uncertainty of 0.19 g/cm 3 calculated from the residuals in the overlap region of scanning mobility and aerodynamic particle sizers. A multi-instrument measurement and quality control scheme is proposed to identify large measurement uncertainties. The extinction and scattering coefficients calculated from the merged fine particle number size distributions by Mie theory are comparable with the measurements from cavity-enhanced albedometer. The differences between the calculated and observed scattering and extinction coefficients are less than 2%. Meanwhile, the deduced aerosol complex refractive index n and k are obtained by minimizing the sum of squared residuals of extinction and scattering coefficients and comparable with the values retrieved from the Sun-sky radiometer CE318 measurements. The correlation coefficient on n is 0.72. However, the correlation on k is not optimized, explained by the influence of anthropogenic aerosol particles with strong absorption near ground and the poor accuracy of k. Compared with independent observations, a good agreement between the optical parameters is also obtained.
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