Partitioning and Mobility of Chromium in Iron-Rich Laterites from an Optimized Sequential Extraction Procedure.

Chromium (Cr) leached from iron (Fe) (oxyhydr)oxide-rich tropical laterites can substantially impact downstream groundwater, ecosystems, and human health. However, its partitioning into mineral hosts, its binding, oxidation state, and potential release are poorly defined. This is in part due to the current lack of well-designed and validated Cr-specific sequential extraction procedures (SEPs) for laterites. To fill this gap, we have (i) first optimized a Cr SEP for Fe (oxyhydr)oxide-rich laterites using synthetic and natural Cr-bearing minerals and laterite references, (ii) used a complementary suite of techniques and critically evaluated existing non-laterite and non-Cr-optimized SEPs, compared to our optimized SEP, and (iii) confirmed the efficiency of our new SEP through analyses of laterites from the Philippines. Our results show that other SEPs inadequately leach Cr host phases and underestimate the Cr fractions. Our SEP recovered up to seven times higher Cr contents because it (a) more efficiently dissolves metal-substituted Fe phases, (b) quantitatively extracts adsorbed Cr, and (c) prevents overestimation of organic Cr in laterites. With this new SEP, we can estimate the mineral-specific Cr fractionation in Fe-rich tropical soils more quantitatively and thus improve our knowledge of the potential environmental impacts of Cr from lateritic areas.

Sustainable removal of hexavalent chromium using graphene oxide - Iron oxide reinforced pectin/polyvinyl alcohol magnetic gel beads.

The study investigated removal of hexavalent chromium Cr (VI) from aqueous solution using graphene oxide­iron oxide reinforced pectin/polyvinyl alcohol magnetic gel beads prepared through co-precipitation and freeze-drying technique. Scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, vibrating sample magnetometer, N2 adsorption-desorption isotherm, and zeta potential are used for characterization. The surface area of magnetic gel beads calculated by BET method was determined to be 100.95 m2/g, significantly higher than that of GO and GO-Fe3O4. The optimum removal efficiency of GO-Fe3O4/Pec/PVA was assessed by batch method at variables such as pH(1-6), adsorption time(0-180 min), and temperature(25-35 °C). Accordingly, 0.2 g GO-Fe3O4/Pec/PVA dose, pH 2, contact time: 120 min at 25 °C were found to be the optimal conditions, and maximum adsorption capacity of GO, GO-Fe3O4 and GO-Fe3O4/Pec/PVA toward Cr(VI) removal was found to be 39.5, 62.5 and 78.55 mg g-1, respectively. Kinetic and isotherm studies indicate adsorption data follow pseudo-second-order kinetic and Langmuir isotherm models. Thermodynamic studies showed adsorption capacities of adsorbents decreased when temperature increased which indicated adsorption for Cr (VI) was an exothermic process. The activation energies were found to be 34.92, 26.57, and 35.23 KJ mol-1 for GO, GO-Fe3O4, and GO-Fe3O4/Pec/PVA, respectively, which illustrated adsorption of Cr(VI) onto the surface of adsorbents was a physical process. The beads exhibit excellent recoverability and reusability over five cycles. Overall, GO-Fe3O4/Pec/PVA demonstrates exceptional adsorption properties and can serve as an efficient, stable, less toxic, and magnetically separable adsorbent for removal of Cr(VI) from aqueous solution.

Microplastics alter Cr accumulation and fruit quality in Cr(VI) contaminated soil-cucumber system during the lifecycle: Insight from rhizosphere bacteria and root metabolism.

Both microplastics and Cr(VI) potentially threaten soil and crops, but little is known about their interaction in the soil-plant system. This study investigated the effect and mechanism of polyethylene (PE), polyamide (PA), and polylactic acid (PLA) microplastics on Cr bioaccumulation and toxicity in a Cr(VI) contaminated soil-cucumber system during the lifecycle. The results show that microplastics had a greater effect on Cr accumulation in cucumber roots, stems, and leaves than in fruits. PE microplastics increased, but PA and PLA microplastics decreased the Cr accumulation in cucumber. Microplastics, especially high-dose, small, and aged microplastics, exacerbated the effects of accumulated Cr in cucumber on fresh weight and fruit yield. The nutrient contents in fruits except soluble sugars were reduced by microplastics. The random forest regression model shows that the microplastic type was the most important factor causing changes in the soil-cucumber system except for Cr(VI) addition. Under Cr(VI) and microplastic co-exposure, bacteria that could simultaneously tolerate Cr(VI) stress and degrade microplastics were enriched in the rhizosphere soil. The partial least squares path model shows that microplastics reduced the beneficial effect of the bacterial community on cucumber growth. Microplastics, especially PLA microplastics, alleviated the adverse effects of Cr(VI) stress on root metabolism.

Microalgae-enhanced bioremediation of Cr(VI) ions using spent coffee ground-derived magnetic biochar MoS2-Ag composites.

Composites of magnetic biochar derived from spent coffee grounds were prepared using MoS2 decorated by plasmonic silver nanoparticles (MoS2-Ag), which were used for the bioremediation Cr6+ ions. The composites were characterized by electron microscopy, X-ray diffraction, Raman, and UV-VIS spectroscopy. The bioremediation of Cr6+ ions was enhanced almost two times compared to microalgae, Spirulina maxima. Such an increased activity is attributed to heterojunction formation of Biochar@MoS2-Ag composite due to the synergetic effects of surface plasmon resonance of AgNPs inducing amplified local electric field, thus simultaneously increasing the absorption of MoS2 under visible or near-infrared light. The combination of Biochar@MoS2-Ag and Spirulina maxima powder was effective for the separation (microalga-based absorption and accumulation of Cr6+ ions) of photo-induced carriers (composite-assisted to breakdown Cr6+ ions). This study offers efficient eco-friendly treatment of Cr6+ ions by reporting the first enhanced bioremediation of Cr(VI) ions by microalgae using MoS2-Ag-modified biochar obtained from consumed coffee grounds.

Effects of chromate on nitrogen removal and microbial community in two-stage vertical-flow constructed wetlands.

Nitrogen and chromium (Cr(VI)) pollution in waterbodies pose great threats to human health, and a cost-effective alternative with Cr(VI) and nitrogen simultaneous removal is still needed. This study investigated the influence of Cr(VI) on nitrogen removal in the two-stage vertical-flow constructed wetlands (TS-VFCWs) along with iron ore and woodchip, and explored relationship between Cr(VI) and nitrogen removal. The results showed that efficient Cr(VI) and nitrogen removal were simultaneously achieved in TS-VFCWs together with iron-ore and woodchip under 2 mg/L-Cr(VI), whereas 10 mg/L-Cr(VI) gave significant and recoverable inhibition of nitrogen removal. Cr(VI) supplementation promoted the beneficiation of Cr(VI)-reducing/resistant bacteria IMCC26207 and Bryobacter on iron-ore. Woodchip enriched Cr(VI)-reducing bacteria Streptomyces and Thiobacillus. XRD and XPS showed that abundant bound-Cr existed in the surface of iron ore and woodchip, and Cr(III) precipitation/oxide was the major product. High abundances of nitrifying and autotrophic/heterotrophic denitrifying bacteria ensured good nitrogen removal at Cr(VI) stress.

Selenium-mediated Cr(VI) reduction and SeNPs synthesis accelerated Bacillus cereus SES to remediate Cr contamination.

Microbial biotransformation of Cr(VI) is a sustainable approach to reduce Cr(VI) toxicity and remediate Cr(VI) contamination. In this study, Bacillus cereus SES with the capability of reducing both Cr(VI) and Se(IV) was isolated, and the effect of Se supplementation on Cr(VI) reduction by Bacillus cereus SES was investigated. Se(IV) addition enabled 2.6-fold faster Cr(VI) reduction, while B. cereus SES reduced 96.96% Se(IV) and produced more selenium nanoparticles (SeNPs) in the presence of Cr(VI). Co-reduction products of B. cereus SES on Cr(VI) and Se(IV) were SeNPs adsorbed with Cr(III). The relevant mechanisms were further revealed by proteomics. Se(IV) supplementation mediated the synthesis of Cr(VI) reductants and stress-resistant substances, thus enhancing Cr(VI) resistance and promoting Cr(VI) reduction. Meanwhile, high Se(IV) reduction rate was associated with Cr(VI)-induced electron transport processes, and Cr(VI) mediated the up-regulation of flagellar assembly, protein export and ABC transporters pathways to synthesis and export more SeNPs. Furthermore, Se combined with B. cereus SES had the potential to reduce the toxicity of Cr(VI) via reducing the bioavailability of Cr and improving the bioavailability of Se in soil. Results suggested that Se could be an efficient strategy to enhance the remediation of B. cereus SES on Cr contamination.

Remediation of Cr(VI)-contaminated soil using self-sustaining smoldering.

Self-sustaining smoldering is an emerging technology for nonaqueous-phase liquid remediation; however, it is rarely applied for Cr(VI)-contaminated soil treatment. In this study, self-sustaining smoldering using rice straw (RS) as a surrogate fuel was applied to remediate Cr(VI)-contaminated soil for the first time. Thirteen one-dimensional vertical smoldering experiments were conducted to investigate the effectiveness of the smoldering method and the effects of key experimental parameters on smoldering remediation performance. Smoldering was observed to be self-sustaining within the range of RS particle size from <0.16 to 2.00-4.00 mm, airflow from 0.2 to 1 m3/h, and Cr(VI)-impacted soil/RS ratios from 2:1 to 6:1. The Cr(VI)-contaminated soil was effectively remediated, which was confirmed by lowered Cr(VI) contents in the treated samples (decreased by 52.22-86.57%) and the elevated fraction of Cr oxidizable and residual form (increased by 1.14-3.30 and 2.97-4.00 times, respectively), compared to the control. The reducing gases (CO and CxHy) generated during the smoldering played a crucial role in the remediation process. The contents of available P and K in the remediated soil containing the remaining biochar and ash increased, thus improving soil reusability. Hence, this study shows that smoldering with RS as supplemental fuel is a promising Cr(VI)-contaminated soil management technique without supplying substantial external energy.

Biorefining of rapeseed meal: A new and sustainable strategy for improving Cr(VI) biosorption on residual wastes from agricultural byproducts after phenolic extraction.

Phenolic recovery from agricultural byproducts has been highlighted due to their health-promoting bioactivities. However, uncontrolled discard of residues after extraction process would induce environmental pollution and bioresource waste. In this study, biorefining of phenolic-rich rapeseed meal (RSM) and its defatted sample (dRSM) was attempted by holistic utilization of phenolic extract and residue separately. Phenolic removal could significantly improve residues' Cr(VI) adsorption capacities by about 21%, which presented extended physical surface and more released functional groups. Moreover, simulating raw material by remixing 3% separated phenolic extracts or main component sinapic acid therein with corresponding residues further improved about 12% adsorption efficiencies. These indicated that the different present forms of phenolics had opposite effects on Cr(VI) removal. While natural conjugational form inhibited hosts' biosorption, free form had enhanced functions for either extract or residue. Four optimal adsorption parameters (pH, adsorbent dosage, contact time and initial Cr(VI) concentration), three kinetic (pseudo-first order, pseudo-second order and intra-particle diffusion) models and two isotherms (Langmuir and Freundlich) were used to reveal the adsorption process. The maximum Cr(VI) adsorption capacity on residues could reach about 100 mg/g, which was superior to that of most biosorbents derived from agricultural byproducts, even some biochar. Together with the residues' advantages with everlasting capacity after 3 adsorption-desorption cycles and excellent abilities for adsorbing multiple co-existed metal ions (Cr(VI), Cd(II), Cu(II), Pb(II), Ni(II) and Zn(II)), phenolic recovery was first proved to be a new and sustainable strategy for modifying biosorbents from agricultural byproducts with zero waste.

Cleanup of Cr(VI)-polluted groundwater using immobilized bacterial consortia via bioreduction mechanisms.

Cr(VI) bioreduction has become a remedial alternative for Cr(VI)-polluted site cleanup. However, lack of appropriate Cr(VI)-bioreducing bacteria limit the field application of the in situ bioremediation process. In this study, two different immobilized Cr(VI)-bioreducing bacterial consortia using novel immobilization agents have been developed for Cr(VI)-polluted groundwater remediation: (1) granular activated carbon (GAC) + silica gel + Cr(VI)-bioreducing bacterial consortia (GSIB), and (2) GAC + sodium alginate (SA) + polyvinyl alcohol (PVA) + Cr(VI)-bioreducing bacterial consortia (GSPB). Moreover, two unique substrates [carbon-based agent (CBA) and emulsified polycolloid substrate (EPS)] were developed and used as the carbon sources for Cr(VI) bioreduction enhancement. The microbial diversity, dominant Cr-bioreducing bacteria, and changes of Cr(VI)-reducing genes (nsfA, yieF, and chrR) were analyzed to assess the effectiveness of Cr(VI) bioreduction. Approximately 99% of Cr(VI) could be bioreduced in microcosms with GSIB and CBA addition after 70 days of operation, which caused increased populations of total bacteria, nsfA, yieF, and chrR from 2.9 × 108 to 2.1 × 1012, 4.2 × 104 to 6.3 × 1011, 4.8 × 104 to 2 × 1011, and 6.9 × 104 to 3.7 × 107 gene copies/L. In microcosms with CBA and suspended bacteria addition (without bacterial immobilization), the Cr(VI) reduction efficiency dropped to 60.3%, indicating that immobilized Cr-bioreducing bacteria supplement could enhance Cr(VI) bioreduction. Supplement of GSPB led to a declined bacterial growth due to the cracking of the materials. The addition of GSIB and CBA could establish a reduced condition, which favored the growth of Cr(VI)-reducing bacteria. The Cr(VI) bioreduction efficiency could be significantly improved through adsorption and bioreduction mechanisms, and production of Cr(OH)3 precipitates confirmed the occurrence of Cr(VI) reduction. The main Cr-bioreducing bacteria included Trichococcus, Escherichia-Shigella, and Lactobacillus. Results suggest that the developed GSIB bioremedial system could be applied to cleanup Cr(VI)-polluted groundwater effectively.

Chromium Speciation by HPLC-DAD/ICP-MS: Simultaneous Hyphenation of Analytical Techniques for Studies of Biomolecules.

The first element legislated adopting chemical speciation was chromium (Cr) for differentiation between the highly toxic Cr(VI) from the micronutrient Cr(III). Therefore, this work aimed to develop a new analytical method through the coupling of High-Performance Liquid Chromatography with Diode-Array Detection (HPLC-DAD) with inductively coupled plasma mass spectrometry (ICP-MS) to obtain molecular and elemental information simultaneously from a single sample injection. In the first step, a low-cost flow split made of acrylic was developed aiming at optimally directing the sample to the detectors, enabling the HPLC-DAD/ICP-MS coupling. After the extraction of Certified Reference Materials (CRM of natural water NIST1640a and sugar cane leaf agro FC_012017), the recoveries determined by ICP-MS were 99.7% and 85.4%, respectively. Then, the method of HPLC-DAD/ICP-MS was applied for real samples of the CRMs. The presence of possible biomolecules associated with Cr(III) and Cr(VI) species was evaluated, with the simultaneous response detection of molecular (DAD) and elementary (ICP-MS) detectors. Potential biomolecules were observed during the monitoring of Cr(VI) and Cr(III) in sugar cane leaves, water samples and a supplement of Cr picolinate. Finally, the article also discusses the potential of the technique applied to biomolecules containing other associated elements and the need of more bioanalytical methods to understand the presence of trace elements in biomolecules.

Synthesis of iron oxide nanoparticles mediated by Camellia sinensis var. Assamica for Cr(VI) adsorption and detoxification.

Environment-benign synthesis of nanoparticles (NPs) are of great importance. Plant-based polyphenols (PPs) are electron donor analytes for the synthesis of metal and metal oxide NPs. This work produced and investigated iron oxide nanoparticles (IONPs) from PPs of tea leaves of Camellia sinensis var. assamica for Cr(VI) removal. The conditions for IONPs synthesis were using RSM CCD and found to be optimum at a time of 48 min, temperature of 26 °C, and iron precursors/leaves extract ratio (v/v) of 0.36. Further, these synthesized IONPs at a dosage of 0.75 g/L, temperature of 25 °C, and pH 2 achieved a maximum of 96% Cr(VI) removal from 40 mg/L of Cr(VI) concentration. The exothermic adsorption process followed the pseudo-second-order model, and Langmuir isotherm estimated a remarkable maximum adsorption capacity (Qm) of 1272 mg g-1 of IONPs. The proposed mechanistic for Cr(VI) removal and detoxification involved adsorption and its reduction to Cr(III), followed by Cr(III)/Fe(III) co-precipitation.

Resistance mechanisms and remediation potential of hexavalent chromium in Pseudomonas sp. strain AN-B15.

The understanding of bacterial resistance to hexavalent chromium [Cr(VI)] are crucial for the enhancement of Cr(VI)-polluted soil bioremediation. However, the mechanisms related to plant-associated bacteria remain largely unclear. In this study, we investigate the resistance mechanisms and remediation potential of Cr(VI) in a plant-associated strain, AN-B15. The results manifested that AN-B15 efficiently reduced Cr(VI) to soluble organo-Cr(III). Specifically, 84.3 % and 56.5 % of Cr(VI) was removed after 48 h in strain-inoculated solutions supplemented with 10 and 20 mg/L Cr(VI) concentrations, respectively. Transcriptome analyses revealed that multiple metabolic systems are responsible for Cr(VI) resistance at the transcriptional level. In response to Cr(VI) exposure, strain AN-B15 up-regulated the genes involved in central metabolism, providing the reducing power by which enzymes (ChrR and azoR) transformed Cr(VI) to Cr(III) in the cytoplasm. Genes involved in the alleviation of oxidative stress and DNA repair were significantly up-regulated to neutralize Cr(VI)-induced toxicity. Additionally, genes involved in organosulfur metabolism and certain ion transporters were up-regulated to counteract the starvation of sulfur, molybdate, iron, and manganese induced by Cr(VI) stress. Furthermore, a hydroponic culture experiment showed that toxicity and uptake of Cr(VI) by plants under Cr(VI) stress were reduced by strain AN-B15. Specifically, strain AN-B15 inoculation increased the fresh weights of the wheat root and shoot by 55.5 % and 18.8 %, respectively, under Cr(VI) stress (5 mg/L). The elucidation of bacterial resistance to Cr(VI) has an important implication for exploiting microorganism for the effective remediation of Cr(VI)-polluted soils.

Tea saponin enhanced bioleaching of Fusarium solani to remove hexavalent chromium from soil.

Hexavalent chromium pollution is one of the most serious types of site pollution. In this study, a microorganism was screened to remove most hexavalent chromium from soil by leaching in 24 h. After ITS sequencing, the microorganism was identified as belonging to the genus Fusarium solani. The optimization experiment of leaching conditions determined that the removal rate reached the maximum 80% when the rotation speed was 200 rpm, the liquid-soil ratio was 15:1, the temperature was 35℃, and the pH was 7. The study has also shown that tea saponin can effectively strengthen the leaching of Fusarium solani to remove hexavalent chromium from the soil. Compared with tea saponin, the strengthening effect of glucose and rhamnolipid was relatively small. The removal rate of hexavalent chromium reached 85% when the added amount of tea saponin was 0.02 g/mL. The leaching solution destroyed part of the iron-manganese nodule structure of the soil, and its hydroxyl, carboxyl, and other groups complexed metal ions into the solution to achieve the purpose of removing hexavalent chromium. However, since the main crystal of the soil was SiO2, there was no obvious change in the XRD of the soil. Toxicity test showed that after leaching, the content of hexavalent chromium leached was 0.28 mg/L (< 1.5 mg/L), which meet the entry standard of the landfill site.

Physiological and Transcriptomic Analysis provide Molecular Insight into 24-Epibrassinolide mediated Cr(VI)-Toxicity Tolerance in Pepper Plants.

The ever-increasing industrial activities over the decades have generated high toxic metals such as chromium (Cr) that hampers plant growth and development. To counter Cr-toxicity, plants have evolved complex defensive systems including hormonal crosstalk with various signaling pathways. 24-epibrassinolide (24-EBR) lowers oxidative stress and alleviates Cr(VI)-toxicity in plants. In this study, the concealed BR-mediated influences on Cr(VI)-stress tolerance were explored by transcriptome analysis in the Capsicum annuum. Results revealed a linkage between plant development under Cr(VI)-stress and the mitigating effect of 24-epibrassinolide and brassinazole. Growth inhibition, chlorophyll degradation, and a significant rise of malondialdehyde (MDA) were observed after 40 mg/L Cr(VI) treatment in Brz supplemented seedlings, whereas 24-EBR supplemented seedlings exhibited commendatory effect. Comparative transcriptome analysis showed that the expression levels of 6687 genes changed (3846 up-regulated and 2841 downregulated) under Cr(VI)-stress with Brz supplementation. Whereas the expression levels of only 1872 genes changed under Cr(VI)-stress with 24-EBR supplementation (1223 up-regulated and 649 downregulated). The functional categories of the differentially expressed genes (DEGs) by gene ontology (GO) revealed that drug transport, defense responses, and drug catabolic process were the considerable enrichments between 24-EBR and Brz supplemented seedlings under Cr(VI)-stress. Furthermore, auxin signaling, glutathione metabolism, ABC transporters, MAPK pathway, and 36 heavy metal-related genes were significantly differentially expressed components between Cr(VI)-stress, 24-EBR, and Brz supplemented seedlings. Overall, our data demonstrate that employing 24-EBR can commendably act as a growth stimulant in plants subjected to Cr(VI)-stress by modulating the physiological and defense regulatory system.

Fabrication of Polyaluminium Ferric Sulfate from Bauxite Residue for Efficient Removal of Cr(VI) from Simulated Wastewater.

Bauxite residue is generated from alumina production in the alumina refining industry by the Bayer process, which requires a large amount of land resource and causes serious environmental problems. In this paper, a novel recycling strategy is proposed to rehabilitate the land and produce the polyaluminium ferric sulfate (PAFS) and siliceous gypsum byproducts from the bauxite residue. The batch experiments reveal that the maximum Cr(VI) removal efficiency of as-prepared PAFS can reach 95.80% with an initial concentration of 10.41 mg/L. In addition, the non-toxic siliceous gypsum should be an ideal raw material for cement plants. Various characterizations (e.g., SEM, FTIR, and XRD) are employed to reveal the mechanism of synthesis PAFS and their Cr(VI) removal performance. Consequently, this paper provides a deep insight into the utilization of bauxite residue as a resource and gives a new strategy for preparing PAFS and gypsum from bauxite residue.

Bioremediation of hexavalent-chromium contaminated groundwater: Microcosm, column, and microbial diversity studies.

Sulfate reducing bacteria (SRB) have the capability of bioreducing hexavalent chromium [Cr(VI)] to trivalent chromium [Cr(III)] under sulfate-reducing conditions for toxicity reduction. However, a high amount of sulfate addition would cause elevated sulfide production, which could inhibit the growth of SRB and result in reduced Cr(VI) bioreduction efficiency. A slow release reagent, viscous carbon and sulfate-releasing colloidal substrates (VCSRCS), was prepared for a long-lasting carbon and sulfate supplement. In the column study, VCSRCS was injected into the column system to form a VCSRCS biobarrier for Cr(VI) containment and bioreduction. A complete Cr(VI) removal was observed via the adsorption and bioreduction mechanisms in the column with VCSRCS addition. Results from X-ray diffractometer analyses indicate that Cr(OH)3(s) and Cr2O3(s) were detected in precipitates, indicating the occurrence of Cr(VI) reduction followed by Cr(III) precipitation. Results from the Fourier-transform infrared spectroscopy analyses show that cell deposits carried functional groups, which could adsorb Cr. Addition of VCSRCS caused increased populations of total bacteria and dsrA, which also enhanced Cr(VI) reduction. Microbial diversity results indicate that VCSRCS addition resulted in the growth of Cr(VI)-reducing bacteria including Exiguobacterium, Citrobacter, Aerococcus, and SRB. Results of this study will be helpful in developing an effective and green VCSRCS biobarrier for the bioremediation of Cr(VI)-polluted groundwater.

Sustainable and Green Synthesis of Waste-Biomass-Derived Carbon Dots for Parallel and Semi-Quantitative Visual Detection of Cr(VI) and Fe3.

Carbon dot (CD)-based multi-mode sensing has drawn much attention owing to its wider application range and higher availability compared with single-mode sensing. Herein, a simple and green methodology to construct a CD-based dual-mode fluorescent sensor from the waste biomass of flowers of wintersweet (FW-CDs) for parallel and semi-quantitative visual detection of Cr(VI) and Fe3+ was firstly reported. The FW-CD fluorescent probe had a high sensitivity to Cr(VI) and Fe3+ with wide ranges of linearity from 0.1 to 60 µM and 0.05 to 100 µM along with low detection limits (LOD) of 0.07 µM and 0.15 µM, respectively. Accordingly, the FW-CD-based dual-mode sensor had an excellent parallel sensing capacity toward Cr(VI) and Fe3+ with high selectivity and strong anti-interference capability by co-using dual-functional integration and dual-masking strategies. The developed parallel sensing platform was successfully applied to Cr(VI) and Fe3+ quantitative detection in real samples with high precision and good recovery. More importantly, a novel FW-CD-based fluorescent hydrogel sensor was fabricated and first applied in the parallel and semi-quantitative visual detection of Cr(VI) and ferrous ions in industrial effluent and iron supplements, further demonstrating the significant advantage of parallel and visual sensing strategies.

Isolation of functional bacterial strains from chromium-contaminated site and bioremediation potentials.

In this study, two Cr(VI)-reducing functional bacterial strains (TJ-1 and TJ-5) were successfully isolated and screened from the chromium-contaminated soil from a real site. The 16S rRNA gene sequences were analysed, which showed high similarity (>99%) with Stenotrophomonas maltophilia (TJ-1) and Brucella intermedius (TJ-5) species. The optimum growth for the two bacteria to reduce Cr(VI) were achieved at pH 7.0 and initial inoculation amount of 5%. The two strains were applied to real contaminated soil samples and showed better Cr removal when external carbon sources were added. Using sawdust as a solid-phase carbon source supplement, both TJ-1 and TJ-5 showed higher remediation efficiency (99.77% and 93.86%) than using glucose as the carbon source (68.56% and 70.87%). Results of the stability of soil Cr(VI) bioremediation revealed that the water-soluble Cr(VI) content of bioremediated sample remained unchanged, indicating that Cr(VI) is not easily released after death of the strains. Solid-phase carbon source supplements may help the cells to attach and grow into biofilms, creating a better growth condition which improved the remediation efficiency. Column experiments showed that the total remediation efficiencies by the two strains were 34.23% and 20.63%, respectively, within a short time period (76 h). Therefore, the two strains showed great bioremediation potentials for chromium-contaminated sites and can be used in future application of in-situ bioremediation.

Tubular Sediment-Water Electrolytic Fuel Cell for Dual-Phase Hexavalent Chromium Reduction.

A novel tubular sediment-water electrolytic fuel cell (SWEFC) was fabricated for the reduction of Cr(VI) in a dual-phase system. The approach simulates a standing water body with Cr(VI)-contaminated overlying water (electrolyte) and bottom sediment phase with electrodes placed in both the phases, supplemented with urea as a potential electron donor. Cr(VI) reduction efficiency of 93.2 ± 1.3% from electrolyte (in 1.5 h) and 81.2 ± 1.3% from the sediment phase (in 8 h) with an initial Cr(VI) concentration of 1,000 mg/L was observed in a single-cell configuration. The effect of initial Cr(VI) concentration, variation in sediment salinity and pH, and different electron donors on the SWEFC performance were systematically investigated. SWEFC showed enhanced performance with 2.4-fold higher current (193.9 mA) at 400 mg/L Cr(VI) concentration when cow dung was used as a low-cost alternative to urea as an electron donor. Furthermore, reactor scalability studies were carried out with nine-anode and nine-cathode configuration (3 L electrolyte and 2 kg sediment), and reduction efficiencies of 98.9 ± 0.9% (in 1 h) and 97.6 ± 2.2% (in 8 h) were observed from the electrolyte and sediment phases, respectively. The proposed sediment-water electrolytic fuel cell can be an advanced and environmentally benign strategy for Cr(VI) remediation from contaminated sediment-water interfaces along with electricity generation.

Removal of Cr(VI) by polyaniline embedded polyvinyl alcohol/sodium alginate beads - Extension from water treatment to soil remediation.

Efficient nano-scale chromium (Cr) remediating agents used in the water industry may find their application in soil difficult because of the strong aggregation effect. In this study, a millimeter-sized PANI/PVA/SA composite (PPS) was synthesized by embedding polyaniline (PANI) into polyvinyl alcohol (PVA)/sodium alginate (SA) gel beads. Additionally, the PPS was used to recover hexavalent chromium (Cr(VI)) contaminated water and soil to study the remediation impacts and mechanism. Results showed that the PPS was an irregular sphere with a pore size of 24.24 nm and exhibited strong adsorption capacity (83.1 mg/g) for removing Cr(VI) in water. The Cr(VI) adsorption by PPS could be well described with the pseudo-second-order kinetics and the Redlich-Peterson isotherm model, indicating that the chemical reactions were the controlling step in the Cr(VI) adsorption process. PPS also exhibited excellent physicochemical properties (< 13 mg/L TOC release) and reusability (efficiency of 95.25% after four runs) for Cr(VI) removal. Soil incubation results showed that the 5% PPS (5PPS) treatment could efficiently remove 24.17% of total Cr and 52.47% of Cr(VI) in the contaminated soil after 30 days. Meanwhile, the water-soluble and the leaching Cr contents were decreased by 43.37% and 61.78% in the 5PPS group, respectively. Elemental speciation by XPS revealed that Cr(VI) removal from solution and soil proceeded mainly by electrostatic attraction, reduction, and complexation/chelation. The study implied that PPS could be a useful amendment to remediate both the Cr(VI)-contaminated water and soil.