富营养化背景下pH值和初始DOC浓度对水铁矿介导的藻源DOM吸附影响

张丽荣; 李婧男; 赵盼; 宋娜; 汪群慧

doi:10.13205/j.hjgc.202605013

富营养化背景下pH值和初始DOC浓度对水铁矿介导的藻源DOM吸附影响

doi: 10.13205/j.hjgc.202605013

张丽荣¹,
李婧男^1, ,,
赵盼¹,
宋娜¹,
汪群慧^1,2

1. 北京科技大学天津学院环境工程系, 天津 301830;
2. 北京科技大学能源与环境工程学院环境工程系, 北京 100083

基金项目:

北京科技大学天津学院一流专业建设项目（YLZY202402）；北京科技大学天津学院新工科课程（2025GKXM02）

详细信息

作者简介:
张丽荣(1988—),女,讲师,主要研究方向为水体生态环境监测、水资源质量安全保障、环保与安全等。beishuiruxin@126.com

通讯作者:
李婧男(1983—),女,教授,主要研究方向为水环境综合治理、生态修复等。leares@126.com

计量
- 文章访问数: 236
- HTML全文浏览量: 90
- PDF下载量: 1
- 被引次数: 0
出版历程
- 收稿日期: 2025-12-10
- 网络出版日期: 2026-06-06
- 刊出日期: 2026-05-01

Effects of pH value and initial DOC concentration on ferrihydrite-mediated adsorption of algal-derived DOM under eutrophication background

1. Department of Environmental Engineering, Tianjin College, University of Science and Technology Beijing, Tianjin 301830, China;
2. Department of Environmental Engineering, College of Energy and Environmental Engineering, University of Science and Technology Beijing, Beijing 100083, China

摘要

摘要: 在全球富营养化加剧的背景下，藻华暴发导致大量藻源溶解性有机质（ADOM）释放和累积，显著影响水体碳循环与污染物迁移。其中，铁矿物（尤其是水铁矿）对溶解性有机质（DOM）的吸附封存被广泛认为是调控其环境归趋的关键过程，然而目前针对ADOM在不同环境条件下的吸附分馏行为尚不清楚。因此，以铜绿微囊藻来源的ADOM为研究对象，系统探究了pH值（2.0~10.0）和初始溶解性有机碳（DOC）浓度（2~100 mg/L）对ADOM在水铁矿上吸附量与吸附选择性的影响，并结合紫外可见光谱（UV-Vis）与三维荧光光谱-平行因子分析（EEM-PARAFAC）揭示了其分馏规律。结果表明，pH和DOC浓度不仅调控ADOM在水铁矿上的吸附量，还对其分馏效应有显著影响。在pH=2.0~7.0时，吸附量随pH升高而增加，在pH=7.0时达到最大值（21.59 mg C/g），pH>7.0后因静电排斥增强而下降。UV-Vis与EEM分析表明，在pH=3.0~9.0时，随着pH升高，水铁矿对芳香性高、分子量较大的发色类DOM（CDOM）组分以及腐殖化程度相对较高、自生源特征强的类蛋白/芳香氨基酸类荧光DOM（FDOM）的选择性分馏作用持续增强。此外，随着DOC浓度的增加，吸附量呈非线性增长，水铁矿对芳香性低、分子质量较大的CDOM以及腐殖化程度较低、自生源特征较强的类蛋白/芳香氨基酸类FDOM的分馏作用持续增强。研究阐明，在富营养化湖泊等ADOM主导的水体中，水铁矿可通过pH和浓度依赖的选择性吸附有效封存ADOM中的活性组分，从而可能对DOM的组成与反应活性产生潜在影响，为深入理解在富营养化水体中铁矿物介导的内源碳封存过程提供了基础数据。
- 藻源溶解性有机质 /
- 水铁矿 /
- 吸附分馏 /
- pH值 /
- 初始浓度 /
- 碳循环
Abstract: Against the backdrop of intensifying global eutrophication， algal blooms trigger substantial releases and accumulation of algal-derived dissolved organic matter （ADOM）， significantly impacting aquatic carbon cycling and pollutant transport. Among these， the adsorption and sequestration of dissolved organic matter （DOM） by iron minerals，particularly ferrihydrite，constitutes a pivotal process regulating its environmental fate. However， the adsorption fractionation behaviors of ADOM under varying environmental conditions remains poorly understood. Consequently， this study systematically investigates the effects of pH （2.0 to 10.0） and initial dissolved organic carbon （DOC） concentration （2 to 100 mg C/L） on the adsorption amount and selectivity of ADOM onto ferrihydrite. The fractionation patterns were elucidated using ultraviolet-visible spectroscopy （UV-Vis） and three-dimensional fluorescence spectroscopy-parallel factor analysis （EEM-PARAFAC）. Results indicate that pH and DOC concentration not only regulated ADOM adsorption onto ferrihydrite but also significantly influenced its fractionation effect. Within the pH range of 2.0 to 7.0， adsorption capacity increased with rising pH， peaking at pH=7.0 （21.59 mg C/g）， declining at pH > 7.0 due to enhanced electrostatic repulsion. UV-Vis and EEM analysis revealed that within the pH range of 3.0 to 9.0， the selective fractionation of ferrihydrite towards highly aromatic， high-molecular-weight chromophoric DOM （CDOM） components and relatively highly humic， biogenic protein-like/aromatic amino acid fluorescent DOM （FDOM） progressively intensified with the increasing pH. Furthermore， with DOC concentration increasing， adsorption capacity exhibited non-linear growth， higher molecular weight components with low aromaticity and lower molecular weight， alongside FDOM of protein-like/aromatic amino acid with lower humification and stronger autotrophic characteristics， progressively intensified. This study demonstrates that in water bodies dominated by ADOM， such as eutrophic lakes， ferrihydrite can effectively sequester the active components of ADOM through pH-dependent and concentration-dependent selective adsorption， which may potentially have an impact on the composition and reactivity of DOM. This can provide fundamental data for a deeper understanding of the autochthonous carbon sequestration process mediated by iron minerals in eutrophic water bodies.
- algal-derived dissolved organic matter /
- ferrihydrite /
- adsorption fractionation /
- pH value /
- initial concentration /
- carbon cycle

HTML全文

参考文献(35)

[1]	HOU X，FENG L，DAI Y，et al. Global mapping reveals increase in lacustrine algal blooms over the past decade［J］. Nature Geoscience，2022，15（2）：130- 134.
[2]	HUANG C，ZHANG Y，HUANG T，et al. Long-term variation of phytoplankton biomass and physiology in Taihu lake as observed via MODIS satellite［J］. Water Research，2019，153：187- 199.
[3]	BAI L，CAO C，WANG C，et al. Roles of phytoplankton-and macrophyte-derived dissolved organic matter in sulfamethazine adsorption on goethite［J］. Environmental Pollution，2017，230：87- 95.
[4]	XU H，LI H，TANG Z，et al. Underestimated methane production triggered by phytoplankton succession in river-reservoir systems:evidence from a microcosm study［J］. Water Research，2020，185：116233.
[5]	ZHOU Y，ZHOU L，ZHANG Y，et al. Autochthonous dissolved organic matter potentially fuels methane ebullition from experimental lakes［J］. Water Research，2019，166：115048.
[6]	LEI P，ZHANG J，ZHU J，et al. Algal organic matter drives methanogen-mediated methylmercury production in water from eutrophic shallow lakes［J］. Environmental Science & Technology，2021，55（15）：10811- 10820.
[7]	LÜ J，ZHANG S，WANG S，et al. Molecular-scale investigation with ESI-FT-ICR-MS on fractionation of dissolved organic matter induced by adsorption on iron oxyhydroxides［J］. Environmental Science & Technology，2016，50（5）：2328- 2336.
[8]	THOMASARRIGO L，KAEGI R，KRETZSCHMAR R. Ferrihydrite growth and transformation in the presence of ferrous iron and model organic ligands［J］. Environmental Science & Technology，2019，53（23）：13636- 13647.
[9]	LALONDE K，MUCCI A，OUELLET A，et al. Preservation of organic matter in sediments promoted by iron［J］. Nature，2012，483（7388）：198- 200.
[10]	KRAMER M，CHADWICK O. Climate-driven thresholds in reactive mineral retention of soil carbon at the global scale［J］. Nature Climate Change，2018，8（12）：1104- 1108.
[11]	CHEN C，DYNES J，WANG J，et al. Properties of Fe-organic matter associations via coprecipitation versus adsorption［J］. Environmental Science & Technology，2014，48（23）：13751- 13759.
[12]	ATEIA M，APUL O，SHIMIZU Y，et al. Elucidating adsorptive fractions of natural organic matter on carbon nanotubes［J］. Environmental Science & Technology，2017，51（12）：7101- 7110.
[13]	COWARD E，OHNO T，PLANTE A. Adsorption and molecular fractionation of dissolved organic matter on iron-bearing mineral matrices of varying crystallinity［J］. Environmental Science & Technology，2018，52（3）：1036- 1044.
[14]	SCHWERTMANN U，CORNELL R. Iron oxides in the laboratory：preparation and characterization［M］. New York：Wiley-VCH，2008.
[15]	CHEN C，MEILE C，WILMOTH J，et al. Influence of pO₂ on iron redox cycling and anaerobic organic carbon mineralization in a humid tropical forest soil［J］. Environmental Science & Technology，2018，52（14）：7709- 7719.
[16]	ZHANG S，YIN Y，YANG P，et al. Using the end-member mixing model to evaluate biogeochemical reactivities of dissolved organic matter（DOM）：autochthonous versus allochthonous origins［J］. Water Research，2023，232：119644.
[17]	CHEN M，KIM S，PARK J，et al. Effects of dissolved organic matter（DOM）sources and nature of solid extraction sorbent on recoverable DOM composition：implication into potential lability of different compound groups［J］. Analytical and Bioanalytical Chemistry，2016，408（17）：4809- 4819.
[18]	GAO J，LIANG C，SHEN G，et al. Spectral characteristics of dissolved organic matter in various agricultural soils throughout China［J］. Chemosphere，2017，176：108- 116.
[19]	LI K，ZHAO B，HAN L，et al. Sediment porewaters serve as a transient organic carbon pool at the land-ocean interface［J］. Water Research，2024，263：122151.
[20]	WANG Z，CAO J，MENG F. Interactions between protein-like and humic-like components in dissolved organic matter revealed by fluorescence quenching［J］. Water Research，2015，68：404- 413.
[21]	COBLE P. Characterization of marine and terrestrial DOM in seawater using excitation-emission matrix spectroscopy［J］. Marine Chemistry，1996，51（4）：325- 346.
[22]	ZHANG Y，LIU X，WANG M，et al. Compositional differences of chromophoric dissolved organic matter derived from phytoplankton and macrophytes［J］. Organic Geochemistry，2013，55：26- 37.
[23]	ZHOU Y，ZHOU J，JEPPESEN E，et al. Will enhanced turbulence in inland waters result in elevated production of autochthonous dissolved organic matter？［J］. Science of the Total Environment，2016，543：405- 415.
[24]	WENG L，VAN RIEMSDIJK W，KOOPAL L，et al. Adsorption of humic substances on goethite：comparison between humic acids and fulvic acids［J］. Environmental Science & Technology，2006，40（24）：7494- 7500.
[25]	HU Z，MCKENNA A M，WEN K，et al. Controls of mineral solubility on adsorption-induced molecular fractionation of dissolved organic matter revealed by 21 T FT-ICR MS［J］. Environmental Science & Technology，2024，58（5）：2313- 2322.
[26]	GONSIOR M，POWERS L，WILLIAMS E，et al. The chemodiversity of algal dissolved organic matter from lysed Microcystis aeruginosa cells and its ability to form disinfection by-products during chlorination［J］. Water Research，2019，155：300- 309.
[27]	ZHU X，WANG K，LIU Z，et al. Probing molecular-level dynamic interactions of dissolved organic matter with iron oxyhydroxide via a coupled microfluidic reactor and an online high-resolution mass spectrometry system［J］. Environmental Science & Technology，2023，57（7）：2981- 2991.
[28]	XU H，JI L，KONG M，et al. Molecular weight-dependent adsorption fractionation of natural organic matter on ferrihydrite colloids in aquatic environment［J］. Chemical Engineering Journal，2019，363：356- 364.
[29]	YE Q，SUN G，WANG Y，et al. Lake reclamation alters molecular-level characteristics of lacustrine dissolved organic matter：A study of nine lakes in the Yangtze Plain，China［J］. Water Research，2022，222：118884.
[30]	HANSEN A，KRAUS T，PELLERIN B，et al. Optical properties of dissolved organic matter（DOM）：Effects of biological and photolytic degradation［J］. Limnology and Oceanography，2016，61（3）：1015- 1032.
[31]	ZHANG H，CUI K，GUO Z，et al. Spatiotemporal variations of spectral characteristics of dissolved organic matter in river flowing into a key drinking water source in China［J］. Science of the Total Environment，2020，700：134360.
[32]	ZUO Y，WU J，CHENG S，et al. Identification of pterins as characteristic humic-like fluorophores released from cyanobacteria and their behavior and fate in natural and engineered water systems［J］. Chemical Engineering Journal，2021，428：131154.
[33]	KONG X，JENDROSSEK T，LUDWICHOWSKI K，et al. Solid-phase extraction of aquatic organic matter：loading-dependent chemical fractionation and self-assembly［J］. Environmental Science & Technology，2021，55（22）：15495- 15504.
[34]	ZHAO B，YAO P，BIANCHI T S，et al. Preferential preservation of pre-aged terrestrial organic carbon by reactive iron in estuarine particles and coastal sediments of a large river-dominated estuary［J］. Geochimica et Cosmochimica Acta，2023，345：34- 49.
[35]	PAN J，FU X，WANG C，et al. Adsorption and molecular weight fractionation of dissolved organic matters with different origins on colloidal surface［J］. Chemosphere，2020，261：127774.