Zhi Dang

Schwertmannite is an important sink for cadmium (Cd) in acid mine drainage (AMD) environments and is unstable when environmental conditions change. However, the release and redistribution of Cd during schwertmannite transformation with respect to pre-bound Cd are poorly understood. In this work, the transformation of cadmium-associated schwertmannite and subsequent Cd repartitioning behaviors were investigated. The way of schwertmannite associated with Cd was predominant by absorption, and the diffuse layer model (DLM) showed that Cd²⁺ existed as monodentate complexes ≡Fe₍₁₎OCd⁺ and ≡Fe₍₂₎OCd⁺ on schwertmannite surfaces. Kinetics of SO₄²⁻ release and mineralogical characterization both showed that the mineral transformation rates decreased and more lepidocrocite aggregated with increasing adsorbed Cd levels. The shrinking core model revealed that Fe(II)-induced process would affect mineral dissolution by changing surface reaction-controlled step to internal diffusion-controlled step, and significantly promote the dissolution rate of Cd-adsorbed schwertmannite. Adsorbed Cd blocked the surface sites for later Fe(II) adsorption and the Fe(II)-Fe(III) electron transfer, then resulted in the decelerated transformation and the accumulation of intermediate phase lepidocrocite. The maximum release of aqueous Cd occurred after 1 mM Fe²⁺ addition, then over 69% of initial added Cd_(aq) re-bound to solid-phase accompanying with mineral transformation, and finally, Cd was mainly associated with the secondary minerals by complexation with surficial OH groups. These findings are useful for developing the strategies for treating Cd contamination in AMD affected areas.

Schwertmannite, a Fe(III)-oxyhydroxysulfate mineral formed in acidic (pH 3~4), iron- and sulfate-rich acid mine drainage (AMD) environments, tends to undergo phase transformations with changes in pH and redox condition, which may depend on the presence of various trace anions and cations. In the present study, the effects of Cu(II) on the stability of arsenate-, chromate-, and molybdate-substituted schwertmannite were investigated. The release of Fe(III) and sulfate from schwertmannite seems to be accelerated in the presence of Cu(II) at pH ~ 3, while Cu(II) retarded the dissolution of schwertmannite at pH ~ 5. XRD and SEM results showed that pure schwertmannite and chromate-substituted schwertmannite underwent transformation to goethite over a 2-month period, the presence of Cu(II) enhanced the stability of the mineral’s structure at both pH 3 and 5. However, the structures of arsenate- and molybdate-substituted schwertmannites showed no significant changes in the presence or absence of Cu(II) at both pH 3 and 5. During the phase transformation process, the amount of released oxyanions followed the sequence of chromate > molybdate > arsenate. Moreover, the release of arsenate and chromate from schwertmannite was retarded in the presence of Cu(II) at pH 5, whereas the release of molybdate was promoted. These results have important environmental implications for the stability of schwertmannite and its potential to immobilize contaminant trace elements under AMD conditions.

Trace-element concentrations in acid mine drainage (AMD) are primarily controlled by the mineralogy at the sediment-water interface. Results are presented for a combined geochemical and mineralogical survey of Dabaoshan Mine, South China. Developed sequential extraction experiments with the analysis of the main mineralogical phases by semi-quantitative XRD, differential X-ray diffraction (DXRD) and scanning electron microscopy (SEM) were conducted to identify the quantitative relationship between iron minerals and heavy metals. Results showed that schwertmannite, jarosite, goethite and ferrihydrite were the dominant Fe-oxyhydroxide minerals which were detected alternately in the surface sediment with the increasing pH from 2.50 to 6.93 along the Hengshi River. Decreasing contents of schwertmannite ranging from 35 wt % to 6.5 wt % were detected along the Hengshi River, which was corresponding to the decreasing metal contents. The easily reducible fractions exert higher affinity of metals while compared with reducible and relatively stable minerals. A qualitative analysis of heavy metals extracted from the sediments indicated that the retention ability varied: Pb > Mn > Zn > As ≈ Cu > Cr > Cd ≈ Ni. Results in this study are avail for understanding the fate and transport of heavy metals associated with iron minerals and establishing the remediation strategies of AMD systems.

Dissolved organic matter (DOM) is an important factor influencing mineral biogeochemistry, although the role of labile DOM in the release of chromium (Cr) from schwertmannite, a mineral with high surface area, is unclear. In this study, the interaction of DOM with synthetic CrO₄²⁻–schwertmannite was investigated to better understand the potential fate of Cr in high‐DOM environments. Minerals and their products were analyzed using Fourier transform infrared spectroscopy, X‐ray diffraction, transmission electron microscopy, scanning electron microscopy, and X‐ray photoelectron spectroscopy. Experiments were conducted at pH 3.2 or 6.5 for different lengths of time, with a shrinking core model developed to describe kinetic processes. The concentration of total Cr in solution reached a maximum when the pH was 6.5 and the concentration of L‐tryptophan was 5 mM. The newly formed minerals were confirmed to be mixtures involving residual schwertmannite, goethite, ferrihydrite, and jarosite. A possible mechanism is proposed to be a ligand‐controlled binary system, accompanied by possible reduction at acidic pH conditions (3.2), including mass transfer and charge transfer processes. This study gives a new perspective for understanding the reactivity and stability of schwertmannite in the environment; it also provides some predictions on the mobility and fate of Cr. These findings will help design remediation strategies for Cr contamination.Core Ideas: The effects of various factors on release of Cr by DOM were considered. A possible mechanism for the release of Cr from schwertmannite was proposed. The time‐dependent product formation has been identified.

The application of modified agricultural wastes for removing polycyclic aromatic hydrocarbons (PAHs) from water is gaining a growing interest. However, most modified methods using synthetic chemicals may cause secondary pollution. To overcome this limitation, in this study, a corn stalk-derived biosorbent (RL-CS) for the removal of phenanthrene (PHE) from aqueous solution was prepared using a rhamnolipid-enhanced acid modification method. RL-CS with higher surface area and lower polarity exhibited higher PHE removal efficiency than that of raw corn stalk (RCS). The adsorption kinetics of RL-CS fitted well with pseudo-second-order kinetics (R² > 0.999). Sorption coefficients and carbon-normalized sorption coefficient of RL-CS were 4.68 and 2.86 times higher than that of RCS. Sorption process of RL-CS was nonlinear. Meanwhile, the sorption was an exothermic process and could occur spontaneously. The present study demonstrated that biosurfactant-modified biosorbent RL-CS may be of great potential for the removal of low concentrations of PAHs from the contaminated waters.

In this study, we have investigated the photolysis of 2,4,4′-tribromophenylphenyl ether (BDE-28) in Triton X-100 (TX-100) solutions, and discussed the effect of anthraquinone-2,6-disulfonate (AQDS) on the photolysis of BDE-28. The effect of TX-100 on the photolysis of BDE-28 was mainly related to the concentration of TX-100. The fastest photolysis of BDE-28 was at 500 mg L⁻¹ of the TX-100 solution, and the corresponding photolysis rate constant was 0.12 min⁻¹. The direct photolysis rate of BDE-28 decreased from 0.17 min⁻¹ to 0.08 min⁻¹ and 0.12 min⁻¹ when NaN₃ and isopropanol were added, respectively. The effect of AQDS on the photolysis of BDE-28 was also mainly related to the concentration of AQDS. When the concentration of AQDS was 0.6 μM, it has a slight influence in promoting the photodegradation of BDE-28; as the AQDS concentrations increased, the suppressing effect was more obvious. AQDS can inhibit the photolysis of BDE-28. Photolysis kinetics and quenching reactions illustrated that BDE-28 can produce a photosensitization reaction in TX-100 solutions, and the effects of AQDS on the photolysis of BDE-28 were mainly dominated by inhibition. In addition to its light shielding effect, AQDS can also combine with BDE-28 and anti-oxidation to inhibit the photolysis of BDE-28. We found that the degradation pathway of BDE-28 was mainly based on de-bromination, and the ions at para positions were preferentially debrominated.