Chromophoric dissolved organic carbon cycle and its molecular compositions and optical properties in precipitation in the Guanzhong basin, China

Abstract

The investigation of water-soluble organic carbon (WSOC), which is important in the biogeochemical cycle of precipitation, can provide a comprehensive view of chromophores within the atmospheric boundary layer. In this work, the optical properties and molecular characteristics of WSOC in precipitation over the Guanzhong Basin (GB) of North China were investigated using ultraviolet-visible (UV–vis) absorption and excitation-emission matrix (EEM) fluorescence spectra, and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) coupled with electrospray ionization (ESI). Furthermore, sources and wet deposition of WSOC were estimated using in-situ measurements and modeling. The light-absorption by WSOC at 250–300 nm (UV region) and 400–550 nm (visible region) was 64.17% and 15.36% relative to the estimated total light-absorption, respectively. Parallel factor (PARAFAC) analysis revealed three types of fluorophores in WSOC at Xi'an (XN), including two humic-like substances (HULIS) and one protein-like substance (PRLIS), with HULIS accounting for 79% of total fluorescence intensity. FT-ICR MS analysis revealed that CHO and CHON were the most abundant components of WSOC at XN, each containing a variety of lignins, protein/amino sugars, and lipids. Moreover, the positive matrix factorization (PMF) model identified the contributions from three main sources (secondary precursors and aerosols, and coal combustion) of WSOC in precipitation at XN. The annual wet deposition flux of WSOC in precipitation at XN was estimated as about 0.63 g C m−2 yr−1, lower than that at other polluted cities. These findings add to our understanding of chromophoric dissolved organic carbon budgets, which is critical for accurately assessing the global carbon cycle.