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Solar ultraviolet (UV) radiation exhibits a significant degradation for dissolved organic matter (DOM) in natural water ecosystems. However, research on photodegradation process of terrestrial components (e.g., humic-like substances) of DOM are limited due to drastic water dilution and rapid degradation. Here, photochemical degradation of terrestrial soil DOM with abundant humic-like substances from different land use were investigated by utilizing spectral technologies. Simulated UV radiation caused obvious losses on concentration, component structures, and fluorescence characteristic of soil DOM samples. The correlations between absorption specific parameters (a280, SUVA254, and SR) and dissolved organic carbon (DOC) were especially pronounced (p < 0.05), which could be used as valid indicators to determine changes in DOM composition and molecular size during photobleaching process. The decreases of DOM fluorescence intensity were corresponded to first-order kinetic and half-life reactions. The greatest reduction on fluorescence intensity (31.56–81.97%) belonged to peak C (i.e., humic-like substances). Overall, DOM from forest and grass soil ecosystems was more easily photochemical degraded than anthropogenic soil DOM. Enhancive contribution of fresh DOM formed by photodegradation increased autochthonous characteristic and bioavailable nutrition by increasing biological index (BIX) values and ammonia nitrogen (NH4+–N) concentration. The slight microbial decomposition effects on DOM happened in unsterilized dark condition. Our findings provided insights for understanding the rapid photodegradation processes of composition and structure of terrestrial DOM. [ABSTRACT FROM AUTHOR]

Dissolved organic matter (DOM) is a ubiquitous group of organic compounds in rainwater that plays vital roles in the biogeochemical cycle. However, little is known about its chemical composition, optical characterization, potential sources, and controlling mechanisms in peri-urban atmospheric rainwater. One-year rainfall samples were collected between September 2018 and August 2019 in a Nanjing suburb. Stoichiometric, ultraviolet–visible (UV–Vis) absorption, and three-dimensional fluorescence excitation-emission matrix (EEM) with parallel factor analysis (PARAFAC) analyses were utilized to characterize DOM. Several proxies for DOM concentration, including dissolved organic carbon (DOC), dissolved organic nitrogen (DON), and absorption coefficient (a254), exhibited power-function relationships with the rainfall amount (r2 = 0.33–0.55, p < 0.001). Particularly, the DOC and a254 value showed significant seasonal variability, with lower value in two wet seasons (winter and summer) than in the dry seasons (autumn and spring). The annual wet depositional (WD) flux of DOC in the Xianlin (XL) site was calculated as 1.68 g C m−2 yr−1, agreeing with the range of global WD flux values. Two terrestrial humic-like components (C1–C2), one microbial humic-like component (C3), and one tryptophan-like component (C4) were identified by EEM-PARAFAC in rainwater DOM. The results of the specific absorption indices (SUVA 254, S R) and PARAFAC component analyses revealed that summer DOM samples had lower fluorescence intensities, aromatic contents, and molecular sizes. Principal component analysis (PCA) based on DOM indices showed that rainwater DOM had predominantly terrestrial humic origins, while this characteristic became slightly weaker in summer. The quantity and quality of rainwater DOM were closely related to meteorological variables (i.e., air mass, rainfall amount, and solar radiation) as well as anthropogenic activities. This study could improve the understanding of the quantity and quality of rainwater DOM on carbon budgets and biogeochemical cycling from some new insights of optical proxies about different fates of rainwater DOM under complex controlling mechanisms. Image 1 • Concentration and chemical structure of rainwater DOM showed seasonal variations. • Climatic factors and human activities were dominant effects on rainwater DOM. • Rainwater DOM components were mainly generated from humic substances. • Wet inorganic N in atmosphere was closely coupled with rainwater DOM. [ABSTRACT FROM AUTHOR]