Glyphosate binding and speciation at the water-goethite interface: a surface complexation model consistent with IR spectroscopy and MO/DFT

IF 11.4 1区环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL

Water Research Pub Date : 2024-12-21 DOI:10.1016/j.watres.2024.123031

Bram Geysels, Tjisse Hiemstra, Jan E. Groenenberg, Rob N.J Comans

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引用次数: 0

Abstract

Binding of glyphosate (PMG) to metal (hydr)oxides controls its availability and mobility in natural waters and soils, and these minerals are often suggested for the removal of PMG from wastewaters. However, a solid mechanistic and quantitative description of the adsorption behavior and surface speciation on these surfaces is still lacking, while it is essential for understanding PMG behavior in aquatic and terrestrial systems. This study gives new insights through advanced surface complexation modeling of new and previously published adsorption data, supplemented with MO/DFT calculations of the geometry, thermochemistry and theoretical infrared (IR) spectra of the surface complexes. PMG complexation by goethite (FeOOH) was measured over a wide range of pH (∼4-10), solution concentration (∼10^-7-10^-3M), and surface loading (∼0.3-3.0 μmol m^-2). Mechanistical modeling using the charge distribution approach revealed the formation of both monodentate and bidentate PMG complexes, each in two protonation states. PMG adsorption is dominated (>60%) by the formation of a bidentate complex having a protonated amino group that deprotonates at high pH and low loading, aligning with previously published ATR-FTIR analyses. Monodentate complexes are less abundant and maintain a protonated amino group over the entire pH range. In addition, the phosphonate group becomes protonated at low pH and high loading. DFT calculations support the role of protons in the surface speciation. The obtained model was able to predict the solution concentration of PMG and its strong pH dependency over the full range in our experiments. Our study provides a new mechanistic and quantitative understanding of PMG binding to goethite, which enables improved predictions of the fate and transport of PMG in and towards natural waters, and provides a framework for optimizing the removal efficiency of PMG with metal (hydr)oxides.

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来源期刊

Water Research 环境科学-工程：环境

CiteScore

20.80

自引率

9.40%

发文量

1307

审稿时长

38 days

期刊介绍： Water Research, along with its open access companion journal Water Research X, serves as a platform for publishing original research papers covering various aspects of the science and technology related to the anthropogenic water cycle, water quality, and its management worldwide. The audience targeted by the journal comprises biologists, chemical engineers, chemists, civil engineers, environmental engineers, limnologists, and microbiologists. The scope of the journal include: •Treatment processes for water and wastewaters (municipal, agricultural, industrial, and on-site treatment), including resource recovery and residuals management; •Urban hydrology including sewer systems, stormwater management, and green infrastructure; •Drinking water treatment and distribution; •Potable and non-potable water reuse; •Sanitation, public health, and risk assessment; •Anaerobic digestion, solid and hazardous waste management, including source characterization and the effects and control of leachates and gaseous emissions; •Contaminants (chemical, microbial, anthropogenic particles such as nanoparticles or microplastics) and related water quality sensing, monitoring, fate, and assessment; •Anthropogenic impacts on inland, tidal, coastal and urban waters, focusing on surface and ground waters, and point and non-point sources of pollution; •Environmental restoration, linked to surface water, groundwater and groundwater remediation; •Analysis of the interfaces between sediments and water, and between water and atmosphere, focusing specifically on anthropogenic impacts; •Mathematical modelling, systems analysis, machine learning, and beneficial use of big data related to the anthropogenic water cycle; •Socio-economic, policy, and regulations studies.