Stabilization of chromium(VI) by hydroxysulfate green rust in chromium(VI)-contaminated soils

doi:10.1016/S1002-0160(21)60009-7

Pedosphere

Volume 31, Issue 4, August 2021, Pages 645-657

https://doi.org/10.1016/S1002-0160(21)60009-7 Get rights and content

Abstract

Chromium (Cr)-contaminated soils pose a great environmental risk, with high solubility and persistent leaching of Cr(VI). In this study, hydroxysulfate green rust (GR_SO4), with the general formula Fe(II)₄Fe(III)₂(OH)₁₂SO₄·8H₂O, was evaluated for its efficiency in Cr(VI) stabilization via Cr(VI) reduction to Cr(III) in four representative Cr(VI)-spiked soils. The initial concentrations of phosphate buffer-extractable Cr(VI) (Cr(VI)_b) in soils 1, 2, 3, and 4 were 382.4, 575.9, 551.3, and 483.7 mg kg^–1, respectively. Reduction of Cr(VI) to Cr(III) by structural Fe(II) (Fe(II)_s) in GR_SO4 in all studied soils was fast, wherein the application of GR_SO4 markedly decreased the amount of Cr(VI)_b at the Cr(VI)_b/Fe(II)_s stoichiometric mole ratio of 0.33. The kinetics of Cr(VI) reduction by GR_SO4 could not be determined as this reaction coincided with the release of Cr(VI) from soil during the experiment. The concentration of Cr(VI)_b decreased, as the Cr(VI)_b/Fe(II)_s ratio decreased from 0.46 to 0.20, generally to below 10 mg kg^–1. Back-transformation of the generated Cr(III) was examined in the presence of manganese oxide birnessite at the birnessite/initial Cr(III) mole ratio of 4.5. The results of batch tests showed that only 5.2% of the initial Cr(III) was converted to Cr(VI) after two months, while under field capacity moisture conditions, less than 0.05% of the initial Cr(III) was oxidized to Cr(VI) after six months. The results illustrated that remediation of Cr(VI)-contaminated soils would be fast, successful, and irreversible with an appropriate quantity of fresh GR_SO4.

References (67)

L Alidokht et al.
Enhanced removal of chromate by graphene-based sulfate and chloride green rust nanocomposites
J Taiwan Inst Chem Eng
(2016)
C Appel et al.
Point of zero charge determination in soils and minerals via traditional methods and detection of electroacoustic mobility
Geoderma
(2003)
M Chrysochoou et al.
Calcium polysulfide treatment of Cr(VI)-contaminated soil
J Hazard Mater
(2010)
X H Feng et al.
Adsorption and redox reactions of heavy metals on synthesized Mn oxide minerals
Environ Pollut
(2007)
J Gao et al.
Scavenging of Cr(VI) from aqueous solutions by sulfide-modified nanoscale zero-valent iron supported by biochar
J Taiwan Inst Chem Eng
(2018)
J M R Génin et al.
Anion and cation distributions in Fe(II–III) hydroxysalt green rusts from XRD and Mössbauer analysis (carbonate, chloride, sulphate, …); the “fougerite” mineral
Solid State Sci
(2004)
R Guilbaud et al.
Surface charge and growth of sulphate and carbonate green rust in aqueous media
Geochim Cosmochim Acta
(2013)
H C B Hansen et al.
Kinetics of nitrate reduction by green rusts—effects of interlayer anion and Fe(II): Fe(III) ratio
Appl Clay Sci
(2001)
R Hassandoost et al.
Hierarchically structured ternary heterojunctions based on Ce³⁺/Ce⁴⁺ modified Fe₃O₄ nanoparticles anchored onto graphene oxide sheets as magnetic visible-light-active photocatalysts for decontamination of oxytetracycline
J Hazard Mater
(2019)
X He et al.
Preparation of Fe(II)–Al layered double hydroxides: Application to the adsorption/reduction of chromium
Colloids Surf A Physicochem Eng Aspects
(2017)

L C Hsu et al.

Comparison of the spectroscopic speciation and chemical fractionation of chromium in contaminated paddy soils

J Hazard Mater

(2015)

I Ikemoto et al.

X-ray photoelectron spectroscopic studies of CrO₂ and some related chromium compounds

J Solid State Chem

(1976)

J Jiang et al.

The mechanism of chromate sorption by three variable charge soils

Chemosphere

(2008)

J Kotaś et al.

Chromium occurrence in the environment and methods of its speciation

Environ Pollut

(2000)

Y J Li et al.

Remediation of hexavalent chromium spiked soil by using synthesized iron sulfide particles

Chemosphere

(2017)

X L Liu et al.

Effects of citrate on hexavalent chromium reduction by structural Fe(II) in nontronite

J Hazard Mater

(2018)

D H Moon et al.

Evaluation of the treatment of chromite ore processing residue by ferrous sulfate and asphalt

J Hazard Mater

(2009)

P H Refait et al.

Mechanisms of formation and structure of green rust one in aqueous corrosion of iron in the presence of chloride ions

Corros Sci

(1998)

C Ruby et al.

Coprecipitation of Fe(II) and Fe(III) cations in sulphated aqueous medium and formation of hydroxysulphate green rust

Solid State Sci

(2003)

C Ruby et al.

Synthesis and transformation of iron-based layered double hydroxides

Appl Clay Sci

(2010)

M Shahid et al.

Chromium speciation, bioavailability, uptake, toxicity and detoxification in soil-plant system: A review

Chemosphere

(2017)

L L Skovbjerg et al.

The mechanisms of reduction of hexavalent chromium by green rust sodium sulphate: Formation of Cr-goethite

Geochim Cosmochim Acta

(2006)

J Sun et al.

Fe(III) photocatalytic reduction of Cr(VI) by low-molecular-weight organic acids with α-OH

J Hazard Mater

(2009)

V Veselská et al.

Chromate adsorption on selected soil minerals: Surface complexation modeling coupled with spectroscopic investigation

J Hazard Mater

(2016)

T Wang et al.

In-situ remediation of hexavalent chromium contaminated groundwater and saturated soil using stabilized iron sulfide nanoparticles

J Environ Manag

(2019)

T Yamashita et al.

Analysis of XPS spectra of Fe²⁺ and Fe³⁺ ions in oxide materials

Appl Surf Sci

(2008)

S T Aldmour et al.

Abiotic reduction of Cr(VI) by humic acids derived from peat and lignite: Kinetics and removal mechanism

Environ Sci Pollut Res

(2019)

L Alidokht et al.

Removal of chromate from aqueous solution by reduction with nanoscale Fe–Al layered double hydroxide

Res Chem Intermed

(2018)

R Bartlett et al.

Behavior of chromium in soils: III. Oxidation

J Environ Qual

(1979)

D L Bond et al.

Kinetics and structural constraints of chromate reduction by green rusts

Environ Sci Technol

(2003)

C A Bower et al.

Exchangeable cation analysis of saline and alkali soils

Soil Sci

(1952)

B D Cullity

Elements of X-ray Diffraction

(1978)

D Dermatas et al.

Ettringite-induced heave in chromite ore processing residue (COPR) upon ferrous sulfate treatment

Environ Sci Technol

(2006)

Cited by (10)

Is Cr(III) re-oxidation occurring in Cr-contaminated soils after remediation: Meta-analysis and machine learning prediction
2024, Journal of Hazardous Materials
Whether Cr(III) in Cr(III)-containing sites formed after Cr(VI) reduction and stabilization remediation are re-oxidized and pose toxicity risks again has been a growing concern. In this study, 1030 data were collected to perform a meta-analysis to clarify the effects of various factors (oxidant type, soil and Cr(III) solid compound properties, aging conditions, and testing methods) on Cr(III) oxidation. We observed that the soil properties of clay, pH ≥ 8, the lower CEC capacity, easily reducible Mn content, and Cr(III) content, and the higher Eh value and Fe content can promote the re-oxidation of Cr(III). Publication bias and sensitivity analyses confirmed the stability and reliability of the meta-analysis. Subsequently, we used five machine learning algorithms to construct and optimize the models. The prediction results of the RF model (RMSE <1.36, R² >0.71) with good algorithm performance showed that after ten years of remediation, the extractable Cr(VI) concentration in the soil was 0.0087 mg/L, indicating a negligible secondary pollution risk of Cr(III) re-oxidation. This study provides theoretical support for subsequent risk management and control after Cr(VI) soil remediation and provides a solution for the quantitative prediction of Cr(III) re-oxidation.
Column experimental study on the removal of hexavalent chromium from water by modified cellulose filter paper loaded with nano zero-valent iron
2024, Journal of Water Process Engineering
Based on our previous batch experimental research, sand column experiments of modified cellulose filter papers loaded with nano zero-valent iron composites (CFP-OH-nZVI) for the removal of hexavalent chromium (Cr(VI)) from porous media water were carried out to discuss and analyze the effects of the initial concentration of Cr(VI) (10, 20, and 40 mg/L), flow rate (1, 3, and 5 mL/min), and adsorbent dosage (0.76, 1.52, and 3.04 g) on the removal of Cr(VI). The Thomas and Yoon-Nelson models have shown good results in fitting and analyzing breakthrough curves. Through column dissection experiments, the elemental valence composition and spatial distribution of Cr and Fe within the column were elucidated, and the mechanism of Cr (VI) removal was analyzed. In addition, the two-site sorption chemical non-equilibrium model in Hydrus-1D effectively simulates the migration behavior of Cr (VI) in composite porous media under different conditions. This study may provide useful reference for the treatment of groundwater contaminated with heavy metals such as Cr (VI) using CFP-OH-nZVI.
Change of soil bacterial communities in chemically stabilized chromium contaminated soils in an accelerated aging experiment
2024, Journal of Environmental Chemical Engineering
Chemical stabilization is a common strategy to clean Cr(VI) contaminated soils. Although many studies have reported both short-term and long-term performance of chemical stabilization, there is no work addressing the impacts of long-term Cr stability on soil bacterial communities after stabilization. In this study, an accelerated aging system that synchronized simulation acid rain leaching and freeze-thaw cycles was established for the first time. We investigated the change of Cr content, environmental variables and bacterial community structure after chemical stabilization by 50-year acid rain leaching and freeze-thaw cycle simulation. Chemical stabilization effectively decreased the content of soil Cr(VI), total Cr in leachate and Cr(VI) in leachate. Different aging conditions altered soil Cr(VI), total Cr in leachate and Cr(VI) in leachate to different extents, hinting at distinct mechanisms of long-term Cr instability between acid rain leaching and freeze-thaw cycle. Cr(VI) and chemical stabilization were identified as the most influential factors affecting soil bacterial community structure, and acid rain leaching and freeze-thaw cycle exhibited considerable but distinct impacts. Our findings provided deeper insights into the long-term restoration of bacterial community in chemically stabilized Cr(VI) contaminated soil and the long-term risk assessment of contaminated soil remediation.
Influence of citrate/tartrate on chromite crystallization behavior and its potential environmental implications
2023, Journal of Hazardous Materials
Citation Excerpt :
Therefore, harmless treatment and resource utilization of chromium pollution has received much attention. Chromium ion usually exists in either Cr(VI) or Cr(III) (Alidokht et al., 2021; Ding et al., 2022). Specifically, Cr(VI) usually exists in the form of HCrO4−, CrO42−, and Cr2O72−, and has a high solubility in water, which makes the Cr(VI) unstable in the environment (Ding et al., 2022; Brasili et al., 2020).
The ferrite process has been developed to purify wastewater containing heavy metal ions and recycle valuable metals by forming chromium ferrite. However, organic matter has an important influence on the crystallization behavior and stability of chromite synthesized from chromium-containing wastewater. We focused on the influence and effect mechanism of two typical organic acid salts (citrate (CA) and tartrate (TA)) on the process of chromium mineralization. It was found that the presence of organic matter leads to the increase of the residual content of Cr in CA system (0.50 mmol/L) and TA system (0.61 mmol/L) in the solution, and the removal of chromium was mainly due to the surface adsorption of Fe(III) hydrolysate. The decreased crystallinity of mineralized products is ascribed to the completion of organic compounds with Fe(II) and Fe(III), which hinders the formation of ferrite precursors. There was bidentate and monodentate chelation between -COO- and metal ions in the CA system and TA system respectively, which resulted in a stronger affinity between CA and iron. This study provides the underlying mechanism for Cr(III) solid oxidation by the ferrite method in an organic matter environment and is of great significance to prevent and control chromium pollution in the environment.
External sodium acetate improved Cr(VI) stabilization in a Cr-spiked soil during chemical-microbial reduction processes: Insights into Cr(VI) reduction performance, microbial community and metabolic functions
2023, Ecotoxicology and Environmental Safety
Interest combined chemical and microbial reduction for Cr(VI) remediation in contaminated sites has greatly increased. However, the effect of external carbon sources on Cr(VI) reduction during chemical-microbial reduction processes has not been studied. Therefore, in this study, the role of external sodium acetate (SA) in improving Cr(VI) reduction and stabilization in a representative Cr(VI)-spiked soils was systemically investigated. The results of batch experiments suggested that the soil Cr(VI) content declined from 1000 mg/kg to 2.6–5.1 mg/kg at 1–5 g C/kg SA supplemented within 15 days of reaction. The external addition of SA resulted in a significant increase in the relative abundances of Cr(VI)-reducing microorganisms, such as Tissierella, Proteiniclasticum and Proteiniclasticum. The relative abundance of Tissierella increased from 9.1% to 29.8% with the SA treatment at 5 g C/kg soil, which was the main contributors to microbial Cr(VI) reduction. Redundancy analysis indicated that pH and SA were the predominant factors affecting the microbial community in the SA treatments at 2 g C/kg soil and 5 g C/kg soil. Functional prediction suggested that the addition of SA had a positive effect on the metabolism of key substances involved in Cr(VI) microbial reduction. This work provides new insightful guidance on Cr(VI) remediation in contaminated soils.
Green ceramsite production via calcination of chromium contaminated soil and the toxic Cr(VI) immobilization mechanisms
2021, Journal of Cleaner Production
Chromium contaminated soil (CCS) is challenging to be disposed because of the high toxicity and mobility of Cr(VI). This paper proposed a way to dispose CCS through calcining ceramsite. Three CCSes and an ordinary soil were selected, and a suitable calcination temperature was determined according to the properties of ceramsite. The stability of Cr(VI) immobilization in ceramsite was investigated and the Cr(VI) immobilization mechanism was analyzed through XRF, XPS, XRD, and BSE. Results showed that all three CCSes could be used to manufacture ceramsite when the calcination temperature was higher than 1100 °C, and the optimal calcination temperature was 1180 °C. The Cr(VI) leaching concentration of ceramsite was much lower than that specified in standard. It was also observed that the calcination temperature should be higher than 1000 °C to ensure the immobilization of Cr(VI). Otherwise, the Cr(VI) leaching concentration would be much higher than that of the original CCS. The Cr(VI) immobilization mechanism of ceramsite was contributed to the transformation of Cr(VI) to Cr(III) and the formation of chromium-bearing mineral, (Mg,Fe)(Cr,Al)₂O₄, as long as the calcining temperature was higher than 1100 °C. This work found that use of CCS in manufacturing ceramsite is a safe way of CCS utilization, but the calcination temperature should be carefully determined. All the results could be potentially referred for the safe and valuable utilization of waste soil.

View all citing articles on Scopus

View full text

Stabilization of chromium(VI) by hydroxysulfate green rust in chromium(VI)-contaminated soils

Abstract

J Taiwan Inst Chem Eng

Geoderma

J Hazard Mater

Environ Pollut

J Taiwan Inst Chem Eng

Solid State Sci

Geochim Cosmochim Acta

Appl Clay Sci

J Hazard Mater

Colloids Surf A Physicochem Eng Aspects

J Hazard Mater

J Solid State Chem

Chemosphere

Environ Pollut

Chemosphere

J Hazard Mater

J Hazard Mater

Corros Sci

Solid State Sci

Appl Clay Sci

Chemosphere

Geochim Cosmochim Acta

J Hazard Mater

J Hazard Mater

J Environ Manag

Appl Surf Sci

Abiotic reduction of Cr(VI) by humic acids derived from peat and lignite: Kinetics and removal mechanism

Environ Sci Pollut Res

Removal of chromate from aqueous solution by reduction with nanoscale Fe–Al layered double hydroxide

Res Chem Intermed

Behavior of chromium in soils: III. Oxidation

J Environ Qual

Kinetics and structural constraints of chromate reduction by green rusts

Environ Sci Technol

Exchangeable cation analysis of saline and alkali soils

Soil Sci

Elements of X-ray Diffraction

Ettringite-induced heave in chromite ore processing residue (COPR) upon ferrous sulfate treatment

Environ Sci Technol