Lignin heterogeneity, involving complex structure and high polydispersity, is a key challenge that restricts its value-added applications. Fractionation of heterogeneous lignin into several homogeneous subdivisions is an attractive and practical strategy to overcome this limitation. In this work, γ-valerolactone (GVL), a sugar-derived product, was used as a green solvent for lignin fractionation when mixed with water. The enzymatic hydrolysis lignin (EHL) was subdivided into three different fractions (F1, F2, and F3) by dissolving it completely in 60% aqueous GVL and then following gradient precipitation in 40%, 30%, and 5% aqueous GVL solutions, sequentially. Detailed characterization techniques were conducted to provide a comprehensive evaluation of the three obtained lignin fractions. Moreover, the proposed fractionation mechanism was further investigated on the basis of Kamlet−Taft parameters. The gel permeation chromatography (GPC) analyses showed that the three fractions presented lower polydispersity than the parent EHL and, furthermore, a gradual decreasing molecular weight due to the different solubility of various molecular weight lignins in aqueous GVL solvents. The structural analyses revealed that with the decrease of molecular weight, the guaiacyl unit content in lignin fractions decreased, with significant increases of functional groups (i.e., aromatic/aliphatic hydroxyl and carboxyl groups). The solvent recycling study showed that the aqueous GVL had a high recovery, and the recycled GVL had the same lignin fractionation performance as fresh GVL. Overall, compared with traditional fractionation using multiple organic solvents, the present work provides a green and efficient route to fractionate lignin and, therefore, significantly decreases its molecular weight polydispersity and structural heterogeneity.
Abstract. Atmospheric models often underestimate particulate sulfate, a major
component in ambient aerosol, suggesting missing sulfate formation
mechanisms in the models. Heterogeneous reactions between SO2 and
aerosol play an important role in particulate sulfate formation and its
physicochemical evolution. Here we study the reactive uptake kinetics of
SO2 onto aerosol containing organic peroxides. We present chamber
studies of SO2 reactive uptake performed under different relative
humidity (RH), particulate peroxide contents, peroxide types, and aerosol
acidities. Using different model organic peroxides mixed with ammonium
sulfate particles, the SO2 uptake coefficient (γSO2) was
found to be exponentially dependent on RH. γSO2 increases
from 10−3 at RH 25 % to 10−2 at RH 71 % as measured for an
organic peroxide with multiple O–O groups. Under similar conditions, the
kinetics in this study were found to be structurally dependent: organic
peroxides with multiple peroxide groups have a higher γSO2 than
those with only one peroxide group, consistent with the reactivity trend
previously observed in the aqueous phase. In addition, γSO2 is linearly related to particle-phase peroxide content, which in turn
depends on gas–particle partitioning of organic peroxides. Aerosol acidity
plays a complex role in determining SO2 uptake rate, influenced by
the effective Henry's Law constant of SO2 and the condensed-phase
kinetics of the peroxide–SO2 reaction in the highly concentrated
aerosol phase. These uptake coefficients are consistently higher than those
calculated from the reaction kinetics in the bulk aqueous phase, and we show
experimental evidence suggesting that other factors, such as particle-phase
ionic strength, can play an essential role in determining the uptake
kinetics. γSO2 values for different types of secondary organic
aerosol (SOA) were measured to be on the order of 10−4. Overall, this
study provides quantitative evidence of the multiphase reactions between
SO2 and organic peroxides, highlighting the important factors that
govern the uptake kinetics.
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