Hydrothermal carbonization process water (HTPW) has been utilized as a substitute for chemical fertilizers in agricultural applications. However, the input of HTPW into paddy water, particularly the significant proportion of dissolved organic matter (DOM) in HTPW (DOM-HTPW), directly engages in photochemical transformations, a phenomenon often overlooked. This study observed a consistent decrease in humification (SUVA280, 7.7-53.9%) and aromaticity (SUVA254, 6.1-40.0%) of DOM-HTPW after irradiation. The primary active photobleaching components of DOM-HTPW varied depending on the feedstock, such as protein for chicken manure DOM-HTPW and lignin for rice straw DOM-HTPW. The photochemical activity of DOM-HTPW was augmented by its lower molecular weight and higher hydrophilic composition, particularly evident in chicken manure DOM-HTPW, which exhibited higher generation rates for 1O2 (35.1-37.1%), 3DOM* (32.8-43.9%), and O2•- (28.6-48.8%) as measured by molecular probes. DOM-HTPW effectively facilitated the phototransformation of tetracycline, with the contribution of O2•- being more significant than 3DOM* and 1O2. These findings shed new light on the understanding the photochemical processes of DOM-HTPW as exogenous DOM and the interconnected fate of contaminants in aquatic environments.

In this study, we investigated the characteristics and herbicidal potential of bispyribac phenolic esters, which belong to the 2-(pyrimidin-2-yloxy)benzoic acid (PYB) class of acetohydroxyacid synthase (AHAS-)-inhibiting herbicides. These herbicides are primarily used for controlling Poaceae and broadleaf weeds. Among them, bispyribac-sodium stands out as a representative in this class. Surprisingly, other bispyribac esters, including alkanol and phenol esters exhibit considerably reduced herbicidal activity compared to bispyribac-sodium. In contrast, oxime esters (e.g., pyribenzoxim) demonstrate high activity. To further understand and develop novel PYB herbicides, we synthesized and screened a series of bispyribac phenolic esters while investigating their photochemical behaviors. Several compounds displayed excellent herbicidal activity, with compounds Ia-19 and Ic showing impressive 90% effective dosages for fresh weight inhibition of barnyard grass, measuring 0.55 and 0.60 g a.i./hm2, respectively. These values were approximately half of bispyribac-sodium or pyribenzoxim. The results indicate that the herbicidal activity of phenolic esters is influenced by both their binding ability to the AHAS enzyme and their decomposition into bispyribac acid. For instance, bispyribac phenol ester exhibited considerably reduced receptor affinity compared to bispyribac-sodium, and faced challenges in transforming into bispyribac acid, explaining its diminished herbicidal activity. However, introducing a photosensitive nitro group led to a complete transformation. This modification improved its affinity with AHAS and accelerated its decomposition into bispyribac acid, further accelerated by photocatalysis. Consequently, nitro-containing compounds displayed heightened herbicidal activity. The findings from this study open possibilities for structural optimization of phenolic esters through quantitative structure-activity relationship analysis, potentially regulating their activity-releasing period. Furthermore, the high activity of aromatic heterocyclic esters offers new insights into developing novel PYB herbicides.

Hydrochar-derived dissolved organic matter (HDOM) enters aquatic ecosystems through soil leaching and surface runoff following the application of hydrochar. However, the photochemical behavior of HDOM remains unclear. The photo-transformation of HDOM was analyzed by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), multiple spectroscopy methods, high-performance liquid chromatography, and combining synchronous fluorescence and Fourier-transform infrared spectroscopy with two-dimensional correlation spectroscopy. The results showed that with the increase of carbonization temperature, amide II in protein-like substances were observed to be preferentially photolyzed, and the protein-like substances were more sensitive to low irradiation time, while the duration time of the photochemical behavior of amide II and aliphatic C-H were more persistent. FT-ICR MS results showed that N and S-containing molecules, including lignins and lipids were more sensitive to ultraviolet irradiation. Furthermore, the photo-transformation of HDOMs was accompanied by the generation of triple excited state dissolved organic matter and singlet oxygen. Our findings will be beneficial for understanding the mechanisms of photo-transformation of HDOM and for predicting the possible behaviors of hydrochar produced at different temperatures before large-scale application.

Substituted polycyclic aromatic hydrocarbons (SPAHs) are a type of emerging pollutant that widely exist in the environment, which also exhibit carcinogenicity, mutagenicity, and teratogenicity. These pollutants belong to toxic pollutants because of their similar structures to polycyclic aromatic hydrocarbons (PAHs). Their environmental behavior and ecological risk have attracted increasing attention. Based on a literature review, we found a new breakthrough in the source, distribution, behavior, and risk of SPAHs with comparison to traditional pollutants PAHs. This paper reviewed the current research progress on the environmental occurrence and photochemical behavior of SPAHs. Their sources, formation mechanisms, and distribution characteristics in the multimedia environment were highlighted, and the photochemical transformation kinetics, pathways, and affecting factors of SPAHs in water, ice, and other media were discussed. Furthermore, the research prospects about the environmental behavior and risk of SPAHs were proposed.

The photochemical activities of three kinds of carbon nanotubes (CNTs) were investigated in the present study. Efficient procedures of dispersing the three kinds of carbon nanotubes in water were established, and the quantitative analysis methods were also developed by TOC-absorbance method. High pH value or low ionic strength of the colloidal solutions facilitated the dispersion of CNTs. The suspensions of three kinds of CNTs could generate singlet oxygen ((1)O2) and hydroxyl radical (•OH) under irradiation of simulated sunlight, while superoxide radical (O2 (•-)) was not detected. The steady-state concentrations of (1)O2 and •OH generated by these CNTs were also determined. The presence of CNTs in natural waters can affect the photochemical behavior of water constituents, such as nitrate, dissolved organic matter, and Fe(3+). Specifically, in nitrate solution, the presence of CNTs could inhibit the generation of •OH by nitrate through light screening effect, while the quenching effect of hydroxyl radicals by CNTs was not observed. Besides light screening effect, the three kinds of CNTs used in the experiments also have a strong inhibiting effect on the ability of DOM to produce •OH by binding to the active sites. Moreover, the adsorption of Fe(3+) on MWCNT-OH and MWCNT-COOH could lead to its inactivation of formation of •OH in acidic conditions. However, the presence of the three kinds of CNTs did not affect the ligand-to-metal charge transfer (LMCT) reaction of DOM-Fe (III) complex.