Unraveling the toxicity response and metabolic compensation mechanism of tannic acid-Cr(III) complex on alga Raphidocelis subcapitata.

Due to their assembly properties and variable molecular weights, the potential biological toxicity effects of macromolecular organic ligand heavy metal complexes are more difficult to predict and their mechanisms are more complex. This study unraveled the toxicity response and metabolic compensation mechanism of tannic acid-Cr(III) (TA-Cr(III)) complex on alga Raphidocelis subcapitata using multi-omics approaches. Results showed TA-Cr(III) complex caused oxidative damage and photosystem disruption, destroying the cell morphology and inhibiting algal growth by >80 % at high exposure levels. TA-Cr(III) complex stress down-regulated proteins linked to proliferation, photosynthesis and antioxidation while upregulating carbon fixation, TCA cycle and amino acid metabolism. The increase of fumarate, citrate, isocitrate and semialdehyde succinate was validated by metabolomics analysis, which improved the TCA cycle, amino acid metabolism and carbon fixation. Activation of the above cellular processes somewhat compensated for the inhibition of algal photosynthesis by TA-Cr(III) complex exposure. In conclusion, physiological toxicity coupled with downstream metabolic compensation in response to Cr(III) complex of macromolecular was characterized in Raphidocelis subcapitata, unveiling the adaptive mechanism of algae under the stress of heavy metal complexes with macromolecular organic ligands.

Immobilization of chromium in real tannery sludge via heat treatment with coal fly ash.

The secure and harmless disposal for Cr-bearing tannery sludge (Cr-TS) has attracted an increasing concern, due to potentially adverse effect on ecosystem and human health. A greener alternative method about "waste treatment with waste" for thermally stabilizing real Cr-TS was developed via employing coal fly ash (CA) as dopants in this research. The co-heat treatment of Cr-TS and CA was carried out at the temperature range of 600-1200 °C to investigate the oxidation of Cr(III), immobilization of chromium and leaching risk of the sintered products, and the mechanism of chromium immobilization was further explored. The results indicate that the doping of CA can significantly inhibit the oxidation of Cr(III) and immobilize chromium by incorporating chromium into spinel and uvarovite microcrystal. At the temperature higher than 1000 °C, most of chromium can be converted into stable crystalline phases. Furthermore, a prolonged leaching test was conducted to study the leaching toxicity of chromium in sintered products, indicating that leaching content of chromium is much less than the regulatory limit. This process is a feasible and promising alternative for immobilization of chromium in Cr-TS. The research findings are supposed to offer a theoretical foundation and strategy choice for thermal stabilization of chromium, as well as safety and harmless disposal of Cr-containing hazardous waste.

Complexation behaviour and removal of organic-Cr(III) complexes from the environment: A review.

Chromium (Cr) is mainly found in the form of organic-Cr(III) complexes in the natural environment and industrial waste. The widespread existence of composite contaminants composed of organic matter (OM) and Cr pose a serious ecological threat, and its potential interaction and removal need to be further summarised. Organic ligands, such as carbohydrates, nitrogen compounds, phenolic compounds, humus substances (HS), and low molecular weight organic acids (LMWOAs), play an important role in governing the speciation, mobility, and absorption and desorption of Cr in the environment. Moreover, growing evidence indicates that oxygen-containing functional groups (e.g., carboxyl, hydroxyl, and phosphate) are closely related to the complexation of Cr(III). Advanced oxidation processes (AOPs) are efficient and widely applicable technologies. However, the re-complexation of oxidation intermediates with Cr(III) and the formation and accumulation of much more toxic Cr(VI) species hinder the possible utilisation of AOPs. In this paper, the sources and harmful effects of organic-Cr(III) complexes are reported in detail. The complexation behaviour and structure of the organic-Cr(III) complexes are also described. Subsequently, the application of AOPs in the decomplexation and degradation of organic-Cr(III) complexes is summarised. This review can be helpful for developing technologies that are more efficient for organic-Cr(III) complex removal and establishing the scientific background for reducing Cr discharge Cr into the environment.

Fenton reaction induced in-situ redox and re-complexation of polyphenol-Cr complex and their products.

In this study, in-situ Fenton oxidation was used for the de-complexation and degradation of tannin-Cr(III) complexes. Cr(III) can be oxidized into free Cr(VI) under the effect of ·OH and oxidation products of tannin can be used as reductant for Cr(VI) to establish a redox cycle of Cr(III)-Cr(VI)-Cr(III). Thus, it is crucial to investigate the interactions of Cr(III) with tannin derived oxidation products due to negligible accumulation of Cr(VI) during Fenton oxidation treatment. Here, sequential filtration/ultrafiltration was applied to reveal the distribution characteristics of TOC and Cr fractions during the oxidation of tannin-Cr(III). As the increase of colloidal size of tannic acid products, residual TOC and Cr mainly distribute in larger size range after the oxidation of tannin-Cr(III) which can be ascribed to re-complexation between oxidation products and Cr(III). Besides, analytical results indicate that carboxyl group and hydroxyl group in oxidation products may cause the re-complexation of Cr(III), resulting in the formation of highly conjugated materials containing Cr(III). It can be concluded that due attention should be paid to the efficient removal technology and mechanism for polymer-Cr complexes, as well as the oxidation intermediates in the role of conversion and removal of Cr species.