Coprecipitation of Fe/Cr Hydroxides at Organic–Water Interfaces: Functional Group Richness and (De)protonation Control Amounts and Compositions of Coprecipitates

Hu, Yandi; Jiang, Xulin; Zhang, Suona; Cai, Dawei; Zhou, Zehao; Liu, Chuan; Zuo, Xiaobing; Lee, Sang Soo

doi:10.1021/acs.est.4c01245

Title: Coprecipitation of Fe/Cr Hydroxides at Organic–Water Interfaces: Functional Group Richness and (De)protonation Control Amounts and Compositions of Coprecipitates

Journal Article · 02 May 2024 · Environmental Science and Technology

DOI: https://doi.org/10.1021/acs.est.4c01245 · OSTI ID:2497725

^[1]; Jiang, Xulin ^[2];

^[2]; Cai, Dawei ^[2];

^[2]; Liu, Chuan ^[2]; Zuo, Xiaobing ^[3];

^[3]

Peking Univ., Beijing (China); Southwest United Graduate School, Kunming (China)
Peking Univ., Beijing (China)
Argonne National Laboratory (ANL), Argonne, IL (United States)

Iron/chromium hydroxide coprecipitation controls the fate and transport of toxic chromium (Cr) in many natural and engineered systems. Organic coatings on soil and engineered surfaces are ubiquitous; however, mechanistic controls of these organic coatings over Fe/Cr hydroxide coprecipitation are poorly understood. Here, Fe/Cr hydroxide coprecipitation was conducted on model organic coatings of humic acid (HA), sodium alginate (SA), and bovine serum albumin (BSA). The organics bonded with SiO₂ through ligand exchange with carboxyl (-COOH), and the adsorbed amounts and pK(a) values of -COOH controlled surface charges of coatings. The adsorbed organic films also had different complexation capacities with Fe/Cr ions and Fe/Cr hydroxide particles, resulting in significant differences in both the amount (on HA > SA(-COOH) >> BSA(-NH₂)) and composition (Cr/Fe molar ratio: on BSA(-NH2) >> HA > SA(-COOH)) of heterogeneous precipitates. Negatively charged -COOH attracted more Fe ions and oligomers of hydrolyzed Fe/Cr species and subsequently promoted heterogeneous precipitation of Fe/Cr hydroxide nanoparticles. Organic coatings containing -NH₂ were positively charged at acidic pH because of the high pK(a) value of the functional group, limiting cation adsorption and formation of coprecipitates. Meanwhile, the higher local pH near the -NH₂ coatings promoted the formation of Cr(OH)₃. Finally, this study advances fundamental understanding of heterogeneous Fe/Cr hydroxide coprecipitation on organics, which is essential for successful Cr remediation and removal in both natural and engineered settings, as well as the synthesis of Cr-doped iron (oxy)hydroxides for material applications.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Natural Science Foundation of China (NSFC); Southwest United Graduate School of Yunnan; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2497725

Journal Information:: Environmental Science and Technology, Journal Name: Environmental Science and Technology Journal Issue: 19 Vol. 58; ISSN 0013-936X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Coprecipitation of Fe/Cr Hydroxides at Organic–Water Interfaces: Functional Group Richness and (De)protonation Control Amounts and Compositions of Coprecipitates

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