In-situ chemical oxidation is an important approach to remediate soils contaminated with persistent organic pollutants, e.g., polycyclic aromatic hydrocarbons (PAHs). However, massive oxidants are added into soils without an explicit model for predicting the redox potential (Eh) during soil remediation, and overdosed oxidants would pose secondary damage by disturbing soil organic matter and acidity. Here, a soil redox potential (Eh) model was first established to quantify the relationship among oxidation parameters, crucial soil properties, and pollutant elimination. The impacts of oxidant types and doses, soil pH, and soil organic carbon contents on soil Eh were systematically clarified in four commonly used oxidation systems (i.e., KMnO4, H2O2, fenton, and persulfate). The relative error of preliminary Eh model was increased from 48-62% to 4-16% after being modified with the soil texture and dissolved organic carbon, and this high accuracy was verified by 12 actual PAHs contaminated soils. Combining the discovered critical oxidation potential (COP) of PAHs, the moderate oxidation process could be regulated by the guidance of the soil Eh model in different soil conditions. Moreover, the product analysis revealed that the hydroxylation of PAHs occurred most frequently when the soil Eh reached their COP, providing a foundation for further microorganism remediation. These results provide a feasible strategy for selecting oxidants and controlling their doses toward moderate oxidation of contaminated soils, which will reduce the consumption of soil organic matter and protect the main structure and function of soil for future utilization. Environmental implications: This study provides a novel insight into the moderate chemical oxidation by the Eh model and largely reduces the secondary risks of excessive oxidation and oxidant residual in ISCO. The moderate oxidation of PAHs could be a first step to decrease their toxicity and increase their bioaccessibility, favoring the microbial degradation of PAHs. Controlling the soil Eh with the established model here could be a promising approach to couple moderate oxidation of organic contaminants with microbial degradation. Such an effective and green soil remediation will largely preserve the soil's functional structure and favor the subsequent utilization of remediated soil.

Brown carbon (BrC) absorbs radiation in the near-UV and visible ranges, affecting atmospheric photochemistry andradiative forcing. Our understanding on the photochemicaltransformation of BrC is still limited, especially when mixed withthe abundant and photochemically labile inorganic salt, nitrate.Herein, we investigate the photochemical reactions of four BrCchromophores, including two methoxyphenols and two nitro-phenols. Experiments were conducted in the absence and presenceof different concentrations of H2O2and nitrate with lights of 254and 313 nm. The results show that the pseudo-first-order decayrate constants (k) of these four BrC compounds at 313 nmillumination were approximately 10 times lower than those at 254nm, demonstrating longer lifetimes of these BrC chromophoresunder tropospherically relevant irradiation. Photo-enhancement in the visible range was observed in most experiments, with thoseunder 313 nm illumination lasting longer, indicating the prolonged effects of nascent and transformed BrC chromophores onradiative forcing. Methoxyphenols had higher averagedkvalues than nitrophenols during direct photolysis with 254 or 313 nmlights, but thekvalues for nitrophenols under high-nitrate (or high-H2O2) conditions approached those of methoxyphenols. Thephoto-enhancement in the visible range for methoxyphenols in the presence of nitrate was substantially contributed by nitroproducts, while that for nitrophenols was mainly contributed by hydroxylated and/or dimerized products. Our results reveal thesimilarity and difference between the photolysis of methoxyphenols and nitrophenols, which may help better understand the aging ofdifferent types of BrC for better model representation of their effects on radiative forcing.

Brown carbon (BrC) absorbs radiation in the near-UV and visible ranges, affecting atmospheric photochemistry and radiative forcing. Our understanding on the photochemical transformation of BrC is still limited, especially when mixed with the abundant and photochemically labile inorganic salt, nitrate. Herein, we investigate the photochemical reactions of four BrC chromophores, including two methoxyphenols and two nitrophenols. Experiments were conducted in the absence and presence of different concentrations of H2O2 and nitrate with lights of 254 and 313 nm. The results show that the pseudo-first-order decay rate constants (k) of these four BrC compounds at 313 nm illumination were approximately 10 times lower than those at 254 nm, demonstrating longer lifetimes of these BrC chromophores under tropospherically relevant irradiation. Photo-enhancement in the visible range was observed in most experiments, with those under 313 nm illumination lasting longer, indicating the prolonged effects of nascent and transformed BrC chromophores on radiative forcing. Methoxyphenols had higher averaged k values than nitrophenols during direct photolysis with 254 or 313 nm lights, but the k values for nitrophenols under high-nitrate (or high-H2O2) conditions approached those of methoxyphenols. The photo-enhancement in the visible range for methoxyphenols in the presence of nitrate was substantially contributed by nitro products, while that for nitrophenols was mainly contributed by hydroxylated and/or dimerized products. Our results reveal the similarity and difference between the photolysis of methoxyphenols and nitrophenols, which may help better understand the aging of different types of BrC for better model representation of their effects on radiative forcing.