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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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2022 The Authors. Published by Elsevier Inc. All rights reserved.)

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., Competing Interests: Declaration of competing interest The authors declare that we have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Various organic compounds extensively used in the leather industry could influence the performance of alkaline precipitation with Cr(III). This study focused on two typical Cr(III)-bearing complexes (Cr(III)-collagen and Cr(III)-citrate) ubiquitous in tannery effluent yet with distinct treatment efficiencies, as Cr(III) was much more difficult to remove in the Cr(III)-citrate solution. Comprehensive analytical methods were employed to explore the intrinsic mechanism. It was found that a lower removal efficiency towards Cr(III) was significantly associated with higher oligomers. The molecular size of the Cr(III)-citrate complex continued to increase with rising pH, making it larger overall than Cr(III)-collagen species. The growing oligomer moiety of dissolved Cr(III)-complex species could persist in the stronger basic pH range, leading to the large amount of residual Cr(III) in the Cr(III)-citrate system. Combining this result with potentiometric titration and X-ray photoelectron spectroscopy data, it was believed that the polymeric species other than monomers facilitated resisting the attack from hydroxide ions, and the postulated Cr(III)-citrate species towards higher oligomers were discovered. Beyond that, both charge neutralization and sweeping effects were presented among the gradually emerging flocs in the Cr(III)-collagen system together with the electric double layer compression effect derived from salinity, thus resulting in a larger floc size and higher Cr(III) removal efficiency in saline solutions., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The application or disposal of char derived from tannery sludge is directly influenced by the mobility and bioavailability of Cr during pyrolysis process. This study focused on the changes of Cr speciation and organic matter in tannery sludge during low-temperature pyrolysis (100-400 °C) to evaluate the toxicity of char in terms of the leaching possibility of Cr. The results showed that (1) lower char yield and more porous structure were observed after pyrolysis. (2) Higher pyrolysis temperature increased Cr content in the char; however, Cr in this case was converted into the residual fraction which minimized its bioavailability therefore lowers its potential risk to the environment. (3) Organic matters in the acid and alkali leachates were mainly humic acid-like substance, and condensed organic matter might appear at 200 °C and then destruct. (4) Despite the comparatively high content of Cr in the char, the leaching toxicity of char was within the security range according to the national standard of China. The Cr content in the acid and alkali leachates decreased to the range of 16.5-35.3 and 0.2-6.8 mg/L, respectively. It was suggested that the potential toxicity of tannery sludge from Cr could be reduced before utilization or disposal by pyrolysis, especially under 400 °C.

During the leather tanning process, chromium (Cr) can interact with different macromolecular organics to generate mixed ligand complexes. The removal of organochromium complexes is one of the main difficulties in the treatment of tannery wastewater. In this study, a gelatin-gallic ac-id-Cr(III) (G-GA-Cr) mixed ligand complex was used to examine the effects of ultrasonic on chromium destabilization and removal from the dissolved complexes. To investigate organic destruction and chromium liberation, alkali precipitation or chelating precipitation assisted with ultrasound were conducted, respectively. The findings demonstrate that ultrasonic-assisted alkali precipitation and chelating precipitation, respectively, removed over 50% and 93% of Cr from the complexes. According to the data, ultrasonication weakened the bonds that bound macromolecular ligands together, and depolymerization took place to the point where Cr could interact directly with hydroxide ions or chelating agents. In addition, by applying ultrasonic-assisted chelating precipitation, the chromium concentration could meet the discharge standard and the amount of precipitation was also noticeably decreased. [ABSTRACT FROM AUTHOR]

Efficient and sustainable treatment of real chromium-containing tannery sludge is attracting an increasing concern due to its potentially severe impacts on eco-system and human-beings. In this study, a greener alternative was studied for the removal and recovery of chromium from tannery sludge by ultrasound-assisted supercritical water oxidation approach. Supercritical water oxidation or ultrasonic treatment was respectively conducted to explore the detailed experiment parameters on organic destruction and chromium liberation. Ultrasound-assisted supercritical water oxidation treatment was then investigated to further explore the mechanism for Cr liberation. Experimental results indicate that supercritical water oxidation or ultrasonic treatment cannot effectively remove Cr from tannery sludge, while almost all Cr (99.6%) will be liberated to supernatant at optimized experimental conditions by ultrasound-assisted supercritical water oxidation treatment, with TOC removal efficiency over 99.9%. This indicates that toxic substances in sludge will be completely removed after ultrasound-assisted supercritical water oxidation treatment, and liberated Cr in the supernatant can be re-utilized after purification. This process is an efficient alternative for toxicity removal and chromium recovery from real tannery sludge contaminated by high concentration of Cr and refractory organics. • Ultrasonic assisted supercritical water oxidation approach is used for tannery sludge treatment. • About 99.9% COD and 99.6% Cr can be simultaneously removed or recovered. • UL pretreatment can facilitate TOC removal and Cr recovery during SCWO treatment. • Cr in sludge can be completely liberated and recovered as Cr 2 O 7 2− after SCWO treatment. [ABSTRACT FROM AUTHOR]

As a hazardous waste, the disposal of chromium enriched tannery sludge has attracted increasing public concern due to its potential adverse risks towards the environment. And incineration is considered to be an effective method to stabilize heavy metals, like Cr, in solid phase during tannery sludge treatment. In this study, real chromium enriched tannery sludge without pre-treatment was incinerated at 300°C–1200 °C under air atmosphere to investigate the transformation of chromium speciation. Here detailed thermal behavior, phase transformation and chromium speciation were characterized by TG-DSC, XRD and XPS, respectively. Experimental results show that content of Cr(VI) increases gradually with the increase of temperature from 300 °C to 500 °C and reaches a maximal level of 46% total Cr at 500 °C, with different Cr(VI) species of CaCrO 4 , MgCrO 4 and Cr 5 O 12. However, the content of Cr(VI) decreases gradually with the further increase of temperature, with only about 5% Cr(VI) at high temperature of 1200 °C, due to formation of Cr(III) species of Cr 2 O 3 crystallite and MgCr 2 O 4 spinel. Besides, a growing number of hexagonally shaped flake-like crystallite Cr 2 O 3 can be discovered from characterization results of XRD and SEM. Finally, the reduction of CaCrO 4 to Cr 2 O 3 in the presence of SiO 2 is thermodynamically feasible over 700 °C, indicating possible transformation of Cr(VI) to Cr(III) through controlled incineration temperature. • Chromium-rich tannery sludge was incinerated under air atmosphere without any pretreatment. • Cr(VI) content reaches a maximal level of 46% of total Cr at 500 °C. • Most of Cr(VI) is gradually reduced to Cr(III) with the temperature increasing over 500 °C. • SiO 2 presented in tannery sludge can induce the reduction of Cr(VI) to Cr(III) above 700 °C. • Main Cr-containing crystalline phases are CaCrO 4 , MgCrO 4 , MgCr 2 O 4 , Cr 5 O 12 and Cr 2 O 3. [ABSTRACT FROM AUTHOR]

It is difficult to completely remove Cr(III) from tannery effluent by alkaline precipitation due to the abundance of strong organic ligands. Thereby, the speciation of the residual Cr after alkaline precipitation is of crucial significance to guide the selection and design of further treatment process. For the first time, we revealed the speciation of the residual Cr with the aid of comprehensive analytical techniques. Results showed that the residual Cr(III) mostly located in two size ranges, i.e. the 13–100 nm fraction and the <4 nm fraction. Combined spectral analyses demonstrated Cr(III) was coordinated by carboxyl groups or hydroxyl groups in both fractions, while the complexation by nitrogen-containing groups was excluded by the total nitrogen and UPLC–MS analysis in the two fractions, respectively. Based on the comprehensive analyses, the structures of Cr(III) complexes in both fractions were proposed. Cr(III) cross-linked the carboxyl groups from polyacrylic acid chains to form the network gel structure in the 13–100 nm fraction, while the complex structure of Cr(III) in the <4 nm fraction was formed through hydroxyl-carboxyl chelation by masking agents such as tartrate and citrate. Although polyoxyethylene ether was abundantly present, it was responsible for the complexation of Cr(III) in neither fraction. [ABSTRACT FROM AUTHOR]