The mixed-phase relative rates approach for determining aerosol particle organic heterogeneous reaction kinetics is often performed utilizing mass spectral tracers as a proxy for particle-phase reactant concentration. However, this approach may be influenced by signal contamination from oxidation products during the experiment. In the current study, the mixed-phase relative rates technique has been improved by combining a positive matrix factor (PMF) analysis with electron ionization aerosol mass spectrometry (unit-mass resolution), thereby removing the influence of m/z fragments from reaction products on the reactant signals. To demonstrate the advantages of this approach, the heterogeneous reaction between OH radicals and citric acid (CA) was investigated using a photochemical flow tube coupled to a compact time-of-flight aerosol mass spectrometer (C-ToF-AMS). The measured heterogeneous rate constant (k(2)) of citric acid toward OH was (3.31 +/- 0.29) x10(-12) cm(3) molecule(-1) s(-1) at 298K and (30 +/- 3) % relative humidity (RH) and was several times greater than the results utilizing individual m/z fragments. This phenomenon was further evaluated for particulate-phase organophosphates (triphenyl phosphate (TPhP), tris-1,3-dichloro-2-propyl phosphate (TDCPP) and tris-2-ethylhexyl phosphate (TEHP)), leading to k(2) values significantly larger than previously reported. The results suggest that heterogeneous kinetics can be significantly underestimated when the structure of the products is highly similar to the reactant and when a non-molecular tracer is measured with a unit-mass resolution aerosol mass spectrometer. The results also suggest that the heterogeneous lifetime of organic aerosol in models can be overestimated due to underestimated OH uptake coefficients. Finally, a comparison of reported rate constants implies that the heterogeneous oxidation of aerosols will be dependent upon a number of factors related to the reaction system, and that a single rate constant for one system cannot be universally applied under all conditions.
Peroxy radical chemistry is the main component of tropospheric chemistry, which is critical for the understanding of essential tropospheric issues such as atmospheric cleansing capacity, photochemical ozone production and secondary organic aerosol formations. Field measurements of peroxy radical concentrations and related analysis with observation based model are the prominent steps to foster the current understanding of peroxy radical chemistry. This paper reviews the state of measurement techniques for peroxy radical, extensively revisits the previous field studies with direct measurements of peroxy radical, outlins the peroxy radical concentrations reported in previous field observations, summarizes the tests of photochemical mechanism with direct field measurement results and discusses the major scientific findings achieved so far. Finally, an outlook for the new directions in the study of atmospheric peroxy radical chemistry is proposed.
The architecture and performance of microbial desalination cell (MDC) have been significantly improved in the past few years. However, the application of MDC is still limited in a scope of small-scale (milliliter) reactors and high-salinity-water desalination. In this study, a large-scale (>10 L) stacked MDC packed with mixed ion-exchange resins was fabricated and operated in the batch mode with a salt concentration of 0.5 g/L NaCl, a typical level of domestic wastewater. With circulation flow rate of 80 mL/min, the stacked resin-packed MDC (SR-MDC) achieved a desalination efficiency of 95.8% and a final effluent concentration of 0.02 g/L in 12 h, which is comparable with the effluent quality of reverse osmosis in terms of salinity. Moreover, the SR-MDC kept a stable desalination performance (>9396) when concentrate volume decreased from 2.4 to 0.1 L (diluate/concentrate volume ratio increased from 1:1 to 1:0.04), where only 0.875 L of nonfresh water was consumed to desalinate 1 L of saline water. In addition, the SR-MDC achieved a considerable desalination rate (95.4 mg/h), suggesting a promising application for secondary effluent desalination through deriving biochemical electricity from wastewater.