Characterizing molecular fingerprint of dissolved organic matter shaped by natural and anthropogenic factors in a large macrophytic shallow lake wetland

Abstract

Dissolved organic matter (DOM) participates in and affects many biological processes in aquatic ecosystems, altering nutrient cycling, bioavailability and toxicity of pollutants. Lake water contains thousands of DOM molecules, which largely originate from natural sources and are greatly influenced by external inputs through anthropogenic activities. To elucidate the shaping mechanism of the DOM composition under complex habitat conditions and anthropogenic disturbances, the characteristic molecular fingerprint of DOM was determined based on chemodiversity information obtained via ultrahigh-resolution mass spectrometry for the Baiyangdian wetland (a typical large macrophytic shallow lake in North China). In the Baiyangdian wetland, the DOM composition exhibited high complexity and spatial heterogeneity, and more recalcitrant DOM molecules were identified in summer than in spring. Although multiple natural factors (nutrient concentration, depth of water and quality of submerged macrophytes) and anthropogenic factors (different land uses and discharge of pollutants) were associated with the relative abundance of various DOM molecules, only the influences from the anthropogenic factors were statistically significant. The alpha diversity index of DOM could reflect variations in both the natural factors (total dissolved phosphorus) and the anthropogenic factors (discharge of nitrogen and phosphorus). Furthermore, the DOM composition in each group were clustered according to the ecological functions (natural reserves, tourism, breeding, and domestic supply functions), and exhibited molecular fingerprint features. This study provides an effective approach to characterize the molecular fingerprint features of DOM and critical information to better understand the shaping mechanism of the DOM composition under complex habitat conditions and anthropogenic disturbances.

Graphical abstract

Keywords

DOM / FT-ICR-MS / Chemodiversity / Habitat / Ecological function / Baiyangdian wetland

Highlight

	● The characteristic molecular fingerprint of DOM was obtained via FT-ICR-MS data.
	● The DOM composition showed high spatial heterogeneity and seasonal variation.
	● Habitat conditions and human activity were related to specific DOM molecules.
	● Significant DOM molecular features occurred in various ecological function areas.

References

[1] Cai Y, Zhang P, Wang Q, Wu Y, Ding Y, Nabi M, Fu C, Wang H, Wang Q. (2023). How does water diversion affect land use change and ecosystem service: a case study of Baiyangdian wetland, China. Journal of Environmental Management, 344: 118558

[2] Chao A, Shen T J. (2003). Nonparametric estimation of Shannon’s index of diversity when there are unseen species in sample. Environmental and Ecological Statistics, 10(4): 429–443

[3] Chipman L, Podgorski D, Green S, Kostka J, Cooper W, Huettel M. (2010). Decomposition of plankton-derived dissolved organic matter in permeable coastal sediments. Limnology and Oceanography, 55(2): 857–871

[4] D’Andrilli J, Cooper W T, Foreman C M, Marshall A G. (2015). An ultrahigh-resolution mass spectrometry index to estimate natural organic matter lability. Rapid Communications in Mass Spectrometry, 29(24): 2385–2401

[5] D’Andrilli J, Foreman C M, Marshall A G, Mcknight D M. (2013). Characterization of IHSS Pony Lake fulvic acid dissolved organic matter by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry and fluorescence spectroscopy. Organic Geochemistry, 65: 19–28

[6] Dittmar T, Koch B, Hertkorn N, Kattner G. (2008). A simple and efficient method for the solid-phase extraction of dissolved organic matter (SPE-DOM) from seawater. Limnology and Oceanography: Methods, 6(6): 230–235

[7] Fang Z, He C, Li Y, Chung K H, Xu C M, Shi Q. (2017). Fractionation and characterization of dissolved organic matter (DOM) in refinery wastewater by revised phase retention and ion-exchange adsorption solid phase extraction followed by ESI FT-ICR MS. Talanta, 162: 466–473

[8] Fu Z, Zhang Y, Jiang X, Guo Y, Wang S. (2021). Risk analysis of impact of human activities on ecological health based on watershed scale: a case study of Hulun. Huanjing Kexue Yanjiu, 34(4): 785–791

[9] Gonsior M, Zwartjes M, Cooper W J, Song W, Ishida K P, Tseng L Y, Jeung M K, Rosso D, Hertkorn N, Schmitt-Kopplin P. (2011). Molecular characterization of effluent organic matter identified by ultrahigh resolution mass spectrometry. Water Research, 45(9): 2943–2953

[10] Han Q, Tong R, Sun W, Zhao Y, Yu J, Wang G, Shrestha S, Jin Y. (2020). Anthropogenic influences on the water quality of the Baiyangdian Lake in North China over the last decade. Science of the Total Environment, 701: 134929

[11] Han Y, Bu H. (2023). The impact of climate change on the water quality of Baiyangdian Lake (China) in the past 30 years (1991–2020). Science of the Total Environment, 870: 161957

[12] Herzsprung P, Kamjunke N, Wilske C, Friese K, Boehrer B, Rinke K, Lechtenfeld O J, Von Tümpling W. (2023). Data evaluation strategy for identification of key molecular formulas in dissolved organic matter as proxies for biogeochemical reactivity based on abundance differences from ultrahigh resolution mass spectrometry. Water Research, 232: 119672

[13] Kellerman A M, Dittmar T, Kothawala D N, Tranvik L J. (2014). Chemodiversity of dissolved organic matter in lakes driven by climate and hydrology. Nature Communications, 5(1): 3804

[14] Kellerman A M, Kothawala D N, Dittmar T, Tranvik L J. (2015). Persistence of dissolved organic matter in lakes related to its molecular characteristics. Nature Geoscience, 8(6): 454–457

[15] Kim S, Kramer R W, Hatcher P G. (2003). Graphical method for analysis of ultrahigh-resolution broadband mass spectra of natural organic matter, the van krevelen diagram. Analytical Chemistry, 75(20): 5336–5344

[16] Koch B P, Dittmar T. (2006). From mass to structure: an aromaticity index for high-resolution mass data of natural organic matter. Rapid Communications in Mass Spectrometry, 20(5): 926–932

[17] Köhler S J, Kothawala D, Futter M N, Liungman O, Tranvik L. (2013). In-lake processes offset increased terrestrial inputs of dissolved organic carbon and color to lakes. PLoS One, 8(8): e70598

[18] Li J, Wang B, Yang M, Li W, Liu N, Qi Y, Liu C Q. (2022). Geographical constraints on chemodiversity of sediment dissolved organic matter in China’s coastal wetlands. Applied Geochemistry, 147: 105506

[19] Li X M, Sun G X, Chen S C, Fang Z, Yuan H Y, Shi Q, Zhu Y G. (2018). Molecular chemodiversity of dissolved organic matter in paddy soils. Environmental Science & Technology, 52(3): 963–971

[20] Liu S, He Z, Tang Z, Liu L, Hou J, Li T, Zhang Y, Shi Q, Giesy J P, Wu F. (2020). Linking the molecular composition of autochthonous dissolved organic matter to source identification for freshwater lake ecosystems by combination of optical spectroscopy and FT-ICR-MS analysis. Science of the Total Environment, 703: 134764

[21] Luo Y Y, Zhang Y Y, Lang M F, Guo X T, Xia T J, Wang T C, Jia H Z, Zhu L Y. (2021). Identification of sources, characteristics and photochemical transformations of dissolved organic matter with EEM-PARAFAC in the Wei River of China. Frontiers of Environmental Science & Engineering, 15(5): 96

[22] Ohno T, He Z, Sleighter R L, Honeycutt C W, Hatcher P G. (2010). Ultrahigh resolution mass spectrometry and indicator species analysis to identify marker components of soil- and plant biomass-derived organic matter fractions. Environmental Science & Technology, 44(22): 8594–8600

[23] Song K, Shang Y, Wen Z, Jacinthe P A, Liu G, Lyu L, Fang C. (2019). Characterization of CDOM in saline and freshwater lakes across China using spectroscopic analysis. Water Research, 150: 403–417

[24] Song C, He H S, Liu K, Du H, Krohn J. (2023). Impact of historical pattern of human activities and natural environment on wetland in Heilongjiang River Basin. Frontiers of Environmental Science & Engineering, 17(12): 151

[25] Wang Y, Gong Z, Zhou H. (2023). Long-term monitoring and phenological analysis of submerged aquatic vegetation in a shallow lake using time-series imagery. Ecological Indicators, 154: 110646

[26] Wen Z, Shang Y, Song K, Liu G, Hou J, Lyu L, Tao H, Li S, He C, Shi Q. . (2022). Composition of dissolved organic matter (DOM) in lakes responds to the trophic state and phytoplankton community succession. Water Research, 224: 119073

[27] Xie R, Xu Y, Ma M, Wang Z. (2022). An integrated screening strategy for novel AhR agonist candidate identification and toxicity confirmation in sediments. Science of the Total Environment, 842: 156816

[28] Xie R, Zhao G, Yang J, Wang Z, Xu Y, Zhang X, Wang Z. (2021). eDNA metabarcoding revealed differential structures of aquatic communities in a dynamic freshwater ecosystem shaped by habitat heterogeneity. Environmental Research, 201: 111602

[29] Xiong Y. (2023). Characterization and variation of dissolved organic matter in composting: a critical review. Frontiers of Environmental Science & Engineering, 17(5): 63

[30] Xu J, He P, Liu C, Wang D, Li D, Wang J, Zhang Y. (2022). Spatial-temporal variations of submersed macrophyte communities and their influencing factors in Lake Baiyangdian. Research of Environmental Sciences, 35(7): 1658–1669

[31] Xu W, Gao Q, He C, Shi Q, Hou Z Q, Zhao H Z. (2020). Using esi ft-icr ms to characterize dissolved organic matter in salt lakes with different salinity. Environmental Science & Technology, 54(20): 12929–12937

[32] Yang K, Zhang Y, Dong Y, Li W. (2017). Selectivity of solid phase extraction for dissolved organic matter in the hypersaline Da Qaidam Lake, China. Environmental Science. Processes & Impacts, 19(11): 1374–1386

[33] Yu H, Xi B D, Shi L L, Tan W B. (2023). Chemodiversity of soil dissolved organic matter affected by contrasting microplastics from different types of polymers. Frontiers of Environmental Science & Engineering, 17(12): 153

[34] Zhou Y, Zhang Y, Jeppesen E, Murphy K R, Shi K, Liu M, Liu X, Zhu G. (2016). Inflow rate-driven changes in the composition and dynamics of chromophoric dissolved organic matter in a large drinking water lake. Water Research, 100: 211–221

[35] Zhou Y, Zhou L, Zhang Y, Zhu G, Qin B, Jang K S, Spencer R G M, Kothawala D N, Jeppesen E, Brookes J D. . (2022). Unraveling the role of anthropogenic and natural drivers in shaping the molecular composition and biolability of dissolved organic matter in non-pristine lakes. Environmental Science & Technology, 56(7): 4655–4664

[36] Zhu J F, Zhou Y, Wang S X, Wang L T, Liu W L, Li H T, Mei J J. (2020). Ecological function evaluation and regionalization in Baiyangdian wetland. Acta Ecologica Sinica, 40(2): 459–472

RIGHTS & PERMISSIONS

Higher Education Press 2025