Modelling the gas–particle partitioning and water uptake of isoprene-derived secondary organic aerosol at high and low relative humidity

This study presents a characterization of the hygroscopic growth behaviour and effects of different inorganic seed particles on the formation of secondary organic aerosols (SOAs) from the dark ozone-initiated oxidation of isoprene at low NOx conditions. We performed simulations of isoprene oxidation using a gas-phase chemical reaction mechanism based on the Master Chemical Mechanism (MCM) in combination with an equilibrium gas–particle partitioning model to predict the SOA concentration. The equilibrium model accounts for non-ideal mixing in liquid phases, including liquid–liquid phase separation (LLPS), and is based on the AIOMFAC (Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients) model for mixture non-ideality and the EVAPORATION (Estimation of VApour Pressure of ORganics, Accounting for Temperature, Intramolecular, and Non-additivity effects) model for pure compound vapour pressures. Measurements from the Cosmics Leaving Outdoor Droplets (CLOUD) chamber experiments, conducted at the European Organization for Nuclear Research (CERN) for isoprene ozonolysis cases, were used to aid in parameterizing the SOA yields at different atmospherically relevant temperatures, relative humidity (RH), and reacted isoprene concentrations. To represent the isoprene-ozonolysis-derived SOA, a selection of organic surrogate species is introduced in the coupled modelling system. The model predicts a single, homogeneously mixed particle phase at all relative humidity levels for SOA formation in the absence of any inorganic seed particles. In the presence of aqueous sulfuric acid or ammonium bisulfate seed particles, the model predicts LLPS to occur below ∼ 80 % RH, where the particles consist of an inorganic-rich liquid phase and an organic-rich liquid phase; however, this includes significant amounts of bisulfate and water partitioned to the organic-rich phase. The measurements show an enhancement in the SOA amounts at 85 % RH, compared to 35 % RH, for both the seed-free and seeded cases. The model predictions of RH-dependent SOA yield enhancements at 85 % RH vs. 35 % RH are 1.80 for a seed-free case, 1.52 for the case with ammonium bisulfate seed, and 1.06 for the case with sulfuric acid seed. Predicted SOA yields are enhanced in the presence of an aqueous inorganic seed, regardless of the seed type (ammonium sulfate, ammonium bisulfate, or sulfuric acid) in comparison with seed-free conditions at the same RH level. We discuss the comparison of model-predicted SOA yields with a selection of other laboratory studies on isoprene SOA formation conducted at different temperatures and for a variety of reacted isoprene concentrations. Those studies were conducted at RH levels at or below 40 % with reported SOA mass yields ranging from 0.3 % up to 9.0 %, indicating considerable variations. A robust feature of our associated gas–particle partitioning calculations covering the whole RH range is the predicted enhancement of SOA yield at high RH (> 80 %) compared to low RH (dry) conditions, which is explained by the effect of particle water uptake and its impact on the equilibrium partitioning of all components.

Status and development for detection and control of ammonium bisulfate as a by-product of SCR denitrification

When denitrification technology using NH3 or urea as the reducing agent is applied to remove NOx from the flue gas, ammonium bisulfate (ABS) by-product will also be generated in the flue gas. ABS has an impact on catalyst life span, denitrification efficiency etc., air preheater and its downstream thermal equipment also have a significant negative impact due to its plugging and corrosion. The requirement for NOx removal efficiency is improved by ultra-low emissions in China. However, wide-load denitrification makes the flue gas composition and temperature changing more complicated. Increasing ammonia injection can improve the NOx removal effect, but too much ammonia injection will lead to the formation of ABS and the increase of deposition risk, the contradiction between these two aspects is amplified by ultra-low emissions and wide-load denitrification in many plants. Coordinating NOx control and reducing the impact of ABS on equipment are issues that the industry needs to solve urgently. In recent years, extensive research on ABS had been carried out deeply, consequently, there has been a relatively in-deepth knowledge foundation for ABS formation, formation temperature, deposition temperature, dew point temperature, decomposition behavior, etc., but the existing researches are insufficient to support the problem of ABS under full load denitrification completely resolved. Therefore, some analysis and detection methods related to ABS are reviewed in this paper, and the impact of ABS on SCR, air preheater and other equipment and the existing research results on reducing the impact of ABS are summarized also. It is hoped that this review will provide a reference for the industry to solve the problems of ABS that hinder wide-load denitrification and affect ultra-low emissions.