Green-synthesized, biochar-supported nZVI from mango kernel residue for aqueous hexavalent chromium removal: Performance, mechanism and regeneration

A biochar-supported green nZVI(G-nZVI@MKB)composite was synthesized using mango kernel waste with“dual identity”as reductant and biomass of biochar.The G-nZVI@MKB with a Fe/C mass ratio of 2.0(G-nZVI@MKB2)was determined as the most favorable composite for hexavalent chromium(Cr(VI))removal.Distinct influencing parameters were discussed,and 99.0%of Cr(VI)removal occurred within 360 min under these optimized parameters.Pseudo-second order kinetic model and intra-particle diffusion model well depicted Cr(VI)removal process.The XRD,FTIR,SEM,and XPS analyses verified the key roles of G-nZVI and functional groups,as well as the primary removal mechanisms involving electrostatic attraction,reduction,and complexation.G-nZVI@MKB2 exhibited good stability and reusability with only a 16.4%decline in Cr(VI)removal after five cycles.This study offered evidence that mango kernel could be recycled as a beneficial resource to synthesize green nZVI-loaded biochar composite for efficient Cr(VI)elimination from water.

Effective Elimination of Hazardous Chromium (VI) Using Periodic Elements and Contemporary Adsorption Methods by Using Magnesium Ferrite Nanoparticle: A Review

A well-known hazardous metal and top contaminant in wastewater is hexavalent chromium. The two forms of most commonly found chromium are chromate ( CrO 4 2− ) and dichromate ( Cr 2 O 7 2− ). Leather tanning, cooling tower blow-down, plating, electroplating, rinse water sources, anodizing baths etc. are the main sources of Cr (VI) contamination. The Cr (VI) is not only non-biodegradable in the environment but also carcinogenic to living population. It is still difficult to treat Cr contaminated waste water effectively, safely, eco-friendly, and economically. As a result, many techniques have been used to treat Cr (VI)-polluted wastewater, including adsorption, chemical precipitation, coagulation, ion-exchange, and filtration. Among these practices, the most practical method is adsorption for the removal of Cr (VI) from aqueous solutions, which has gained widespread acceptance due to the ease of use and affordability of the equipment and adsorbent. It has been revealed that Fe-based adsorbents’ oxides and hydroxides have high adsorptive potential to lower Cr (VI) content below the advised threshold. Fe-based adsorbents were also discovered to be relatively cheap and toxic-free in Cr (VI) treatment. Fe-based adsorbents are commonly utilized in industry. It has been discovered that nanoparticles of Fe-, Ti-, and Cu-based adsorbents have a better capacity to remove Cr (VI). Cr (VI) was effectively removed from contaminated water using mixed element-based adsorbents (Fe-Mn, Fe-Ti, Fe-Cu, Fe-Zr, Fe-Cu-Y, Fe-Mg, etc.). Initial findings suggest that Cr (VI) removal from wastewater may be accomplished by using magnesium ferrite nanomaterials as an efficient adsorbent.

Investigation of Hexavalent Chromium Reduction in Strong Saline and Acidic Nitro-Phosphate Solutions

Phosphorus fertilizers from less pure sedimentary sources become increasingly important, due to depletion of phosphorus from igneous rock of high quality. Consequently, robust methods with potential to remove various types of hazardous elements are required. Among such impurities, hexavalent chromium (Cr(VI)) is very likely to become a future challenge. Different industrial ways to treat phosphate rock are currently being practised, and we have here studied how chromium behaves when using the nitro-phosphate process. The reduction mechanism of Cr (VI) in nitric acid and phosphoric acid solutions was investigated by measuring redox potential and UV-VIS spectra. The results show that Cr (VI) is not stable in strong nitric acid solutions. Reduction of Cr (VI) species decreased with decreasing temperature, NO2 concentration, ionic strength and absence of light. These findings support the proposed reduction reaction:The reduction rate was observed proportional to the nitric acid decomposition: .

Behaviors of vanadium and chromium in coal-based direct reduction of high-chromium vanadium-bearing titanomagnetite concentrates followed by magnetic separation

The reduction behaviors of FeO·V2O3 and FeO·Cr2O3 during coal-based direct reduction have a decisive impact on the efficient utilization of high-chromium vanadium-bearing titanomagnetite concentrates. The effects of molar ratio of C to Fe n(C)/n(Fe) and temperature on the behaviors of vanadium and chromium during direct reduction and magnetic separation were investigated. The reduced samples were characterized by X-ray diffraction(XRD), scanning election microscopy(SEM) and energy dispersive spectrometry(EDS) techniques. Experimental results indicate that the recoveries of vanadium and chromium rapidly increase from 10.0% and 9.6% to 45.3% and 74.3%, respectively, as the n(C)/n(Fe) increases from 0.8 to 1.4. At n(C)/n(Fe) of 0.8, the recoveries of vanadium and chromium are always lower than 10.0% in the whole temperature range of 1100-1250 °C. However, at n(C)/n(Fe) of 1.2, the recoveries of vanadium and chromium considerably increase from 17.8% and 33.8% to 42.4% and 76.0%, respectively, as the temperature increases from 1100 °C to 1250 °C. At n(C)/n(Fe) lower than 0.8, most of the FeO·V2O3 and FeO·Cr2O3 are not reduced to carbides because of the lack of carbonaceous reductants, and the temperature has little effect on the reduction behaviors of FeO·V2O3 and FeO·Cr2O3, resulting in very low recoveries of vanadium and chromium during magnetic separation. However, at higher n(C)/n(Fe), the reduction rates of FeO·V2O3 and FeO·Cr2O3 increase significatly because of the excess amount of carbonaceous reductants. Moreover, higher temperatures largely induce the reduction of FeO·V2O3 and FeO·Cr2O3 to carbides. The newly formed carbides are then dissolved in the γ(FCC) phase, and recovered accompanied with the metallic iron during magnetic separation.

Effect of Cr2O3 addition on oxidation induration and reduction swelling behavior of chromium-bearing vanadium titanomagnetite pellets with simulated coke oven gas

The oxidation induration and reduction swelling behavior of chromium-bearing vanadium titanomagnetite pellets(CVTP)with Cr2O3 addition were studied,and the reduction swelling index(RSI)and compressive strength(CS)of the reduced CVTP with simulated coke oven gas(COG)injection were investigated.The results showed that the CS of the CVTP decreases and the porosity of the CVTP increases with increasing amount of Cr2O3 added.The Cr2O3 mainly exists in the form of(Cr,Fe)2O3 solid solution in the CVTP and as Fe-Cr in the reduced CVTP.The CS of the reduced CVTP increases and the RSI of the reduced CVTP decreases with increasing amount of Cr2O3 added.The limited aggregation and diffusion of metallic iron contribute to the formation of dense lamellar crystals,which leads to the slight decrease for reduction swelling behavior of reduced CVTP.This work provides a theoretical and technical basis for the utilization of CVTP and other Cr-bearing ores such as chromite with COG recycling technology.

Catalysis of Manganese(II) on Chromium(VI) Reduction by Citrate

The catalysis of manganese（Ⅱ） （Mn^2＋） on chromium（Ⅵ） （Cr^6＋） reduction by citrate was studied through batch experiments with the concentration of citrate greatly in excess of Cr^6＋ at 25 ℃ and in pH ranges of 4.0 go 5.0. Results showed that at pH 4.5 within 22 h direct reduction of Cr^6＋ by citrate was not observed, bug for the same time when Mn^2＋ （50 to 200 μmol L^-1） was added, nearly all Cr^6＋ was reduced, with the higher initial Mn^2＋ concentration having faster Cr^6＋ reduction. In the initial stage of the reaction, the Cr^6＋ reduction could be described with a pseudo-first-order kinetics equation. In the lager stage of the reaction, plots of lnc（Cr^6＋） versus t, where c（Cr^6＋） is the Cr^6＋ concentration in the reaction and t is the reaction time, deviated from the initial linear trend. The deviations suggested that the pseudo-first-order kinetics did not apply go the whole experimental period and that some reaction intermediates could have greatly accelerated Cr^6＋ reduction by citrate. The catalysis of the intermediates increased with the reaction time and gradually reached stability. Then, the plot of lnc（Cr^6＋） versus t in the presence of Mn^2＋ was linear again, with the rate constant increasing by 102 times compared with the absence of Mn^2＋. Complexation between Mn^2＋ and citrate was likely a prerequisite for the catalysis of Mn^2＋ on the reaction. Additional experiments showed that introducing eghylenediaminegegraacegic acid （EDTA） into the reaction system strongly suppressed the catalysis of Mn^2＋.

基于绿色生物质阿拉伯树脂的氮掺杂碳点用于检测工业废水中的Cr(VI)

以绿色生物质阿拉伯树脂(AG)为碳源,三羟甲基氨基甲烷(Tris)为氮源,二者按质量比1∶4混合,通过水热法制备了一种新型氮掺杂碳点(NACDs),并基于NACDs构建了一种荧光传感器,用于工业废水中Cr(VI)的检测。取200μL样品溶液、NACDs溶液100μL、0.2 mmol·L^(-1)磷酸氢二钠-磷酸二氢钠缓冲液(pH 8.0) 200μL加至2 mLEP管中,用水定容至1 mL。室温反应10 min后,在激发波长365 nm处扫描,并在430 nm处测量体系荧光强度。结果表明,在365 nm的激发波长下,NACDs于430 nm表现出强荧光信号,并可被Cr(VI)选择性猝灭。Cr(VI)的质量浓度在0.25~3.00 mg·L^(-1)内与NACDs的荧光猝灭值呈线性关系,检出限(3s/k)为0.13 mg·L^(-1)。按照标准加入法对模拟工业废水样品进行回收试验,回收率为103%~105%,测定值的相对标准偏差(n=6)均小于3.0%,加标样品所得测定结果与国家标准方法GB/T 15555.4—1995的无显著性差异。

Removal of Chromium from Chromium（VI） Solutions by Adsorption and Reduction Using Immobilized Persimmon Gel

The removal of chromium（Vl） from an aqueous solution using persimmon gel was examined. The amount of chromium（VI） removed was strongly affected by the pH of the solution, with all ehromium（VI） being removed at pH 2 or lower. However, in a solution containing, 15 mg dry weight of immobilized persimmon gel, the amount of removed chromium（VI） decreased as the pH increased. A part of chromium（VI） was reduced another oxidation stage, mainly chromium（III）, by immobilized persimmon gel. The amount of reduced chromium（III） in the solution was increased with decreasing the pH of the solution. As a result, the amount of total chromium removed was maximal at pH 2. The amount of chromium removed were affected by the chromium concentration and the amount of gel. The maximal amount of chromium removed by the column system was also discussed.

电纺丝制备磁性单晶BiFeO_(3)纳米纤维并用于Cr(VI)的可见光催化还原

本工作提出一种将溶胶凝胶与静电纺丝结合的分步快速烧结技术,成功制备了单晶BiFeO_(3)纳米纤维。通过热重差热分析(TG-DTG)、XRD、SEM、TEM、EDS、紫外可见漫反射光谱和氮气吸附脱附曲线等测试对所制备材料的结构和形貌进行表征。同时,考察了BiFeO_(3)纳米纤维在可见光下对水中Cr(VI)的光催化还原性能。结果显示,相比于传统方式制备的纳米颗粒,该材料因更大的比表面积而具有更高的光催化活性。空穴消耗剂酒石酸的加入能够促进该材料对Cr(VI)的光催化还原反应,使还原效率提高87%。总之,本文制备的BiFeO_(3)材料能在可见光下响应,并在常温下具有弱磁性,能通过磁场力回收,在环境净化领域具有广阔的应用前景。

Synergism of solar-driven interfacial evaporation and photo-Fenton Cr(Ⅵ) reduction by sustainable Bi-MOF-based evaporator from waste polyester

The integration of interfacial solar steam generation and photocatalytic degradation technology has pro-vided a promising platform to simultaneously produce freshwater and degrade pollutants.However,con-structing low-cost,multi-functional evaporators for treating Cr(Ⅵ)-polluted water remains challenging,and the synergistic mechanism on Cr(Ⅵ)reduction is fuzzy.Herein,we propose the combined strategy of ball milling and solution mixing for the sustainable production of Bi-MOF microrod from waste poly(ethylene terephthalate),and construct Bi-MOF-based solar evaporators for simultaneous photo-Fenton Cr(Ⅵ)reduction and freshwater production.Firstly,the evaporator comprised of Bi-MOF microrod and graphene nanosheet possesses high light absorption,efficient photothermal conversion,and good hydro-philic property.Attributing to the advantages,the hybrid evaporator exhibits the evaporation rate of 2.16 kg m^(-2) h^(-1) and evaporation efficiency of 87.5%under 1 kW m^(-2) of irradiation.When integrating with photo-Fenton reaction,the Cr(Ⅵ)reduction efficiency is 91.3%,along with the reaction kinetics of 0.0548 min^(-1),surpassing many advanced catalysts.In the outdoor freshwater production and Cr(Ⅵ)reduction,the daily accumulative water yield is 5.17 kg m^(-2) h^(-1),and the Cr(Ⅵ)reduction efficiency is 99.9%.Furthermore,we prove that the localization effect derived from the interfacial solar-driven evap-oration enhances H_(2)O_(2) activation for the photo-Fenton reduction of Cr(Ⅵ).Based on the result of density functional theory,Bi-MOF microrod provides rich active centers for H_(2)O_(2) activation to produce active sites such as e-or-O_(2).This study not only proposes a new strategy to construct multi-functional solar evaporators for freshwater production and catalytic reduction of pollutants,but also advances the chem-ical upcycling of waste polyesters.

Bi_(2)S_(3)/NiS复合催化剂光催化还原Cr(VI)的研究

通过水热法制备了一种新型Bi_(2)S_(3)/NiS复合光催化剂,采用FT-IR、XRD、SEM、固体荧光和固体紫外等光谱对催化剂的组成、结构、形貌和光学性质进行了表征.Bi_(2)S_(3)/NiS复合催化剂在可见光照射下能有效将溶液中的Cr(VI)光催化还原为Cr(III).在最优条件下,复合催化剂的反应速率常数约为Bi_(2)S_(3)或NiS的反应速率常数的10倍.复合催化剂光催化还原Cr(VI)效率的提高主要是因为Bi_(2)S_(3)和NiS的复合降低了禁带宽度,扩大了光吸收范围,并且复合后有效降低了光生载流子的复合效率.催化剂循环实验表明Bi_(2)S_(3)/NiS复合催化剂具有良好的光学稳定性.研究结果为光催化处理含Cr(VI)废水的材料合成和设计研究提供了参考.

Carburization of ferrochromium metals in chromium ore fines containing coal during voluminal reduction by microwave heating

Chromium ore fines containing coal (COFCC) can be rapidly heated by microwave to conduct the voluminal reduction, which lays a foundation of getting sponge ferrochromium powders with a lower content of C. Under the conditions of COFCC with n(O)-n(C) (molar ratio) as 1.00-0.84 and n(SiO2)-n(CaO) as 1.00-0.39, the samples were heated by 10 kW microwave power to reach the given temperatures and held for different times respectively. The results show that the low-C-Cr ferrochromium metal phase in the reduced materials forms before the high-C-Cr ferrochromium metal phase does. With increasing temperature the C content of ferrochromium metals is in a positive correlation with the content of Cr. The C content of ferrochromium metal in reduced materials is 0-10.07% with an average value of 4.68%. With the increase of holding time the Cr content in ferrochromium metals is in a negative correlation with the content of C, while the content of Fe changes in the contrary way. In the microwave field the kinetic conditions of carburization are closely related with the temperature of microwave heating, holding time and carbon fitting ratio.

Chromium phosphide nanoparticles embedded in porous nitrogen-/phosphorus-doped carbon as efficient electrocatalysts for a nitrogen reduction reaction

The resource recovery of heavy metals from effluent has significant environmental implications and potential commercial value.Chromium phosphide nanoparticles embedded in a nitrogen-/phosphorus-doped porous carbon matrix(CrP/NPC)are synthesized via a consecutive Cr^(6+)leachate treatment and resource recovery process.Electrochemical testing shows that CrP/NPC shows excellent nitrogen reduction reaction(NRR)performance,which yields the highest NH_(3) production rate of 22.56μg h^(−1) mg^(−1)_(cat).and Faradaic efficiency(16.37%)at−0.5 V versus the reversible hydrogen electrode in a 0.05M Na_(2)SO_(4) aqueous solution,as well as robust catalytic stability.The isotopic experiments using ^(15)N^(2) as a nitrogen source confirm that the detected NH_(3) is derived from the NRR process.Finally,density functional theory(DFT)calculations show that the electron deficiency environment of the Cr site can significantly reduce the barrier of the NRR process and promote the formation of intermediate species.

Bifunctional TiO2 Catalysts for Efficient Cr（VI） Photoreduction Under Solar Light Irradiation Without Addition of Acids

Bifunctional TiO2 photocatalysts co-doped with nitrogen and sulfur were prepared by the controlled thermal decomposition of ammonium titanyl sulfate precursor. They have both photocatalytic activity and Brφnsted acidity, and thus are active in the photoreduction of Cr（VI） under solar light irradiation without the addition of acids. The activity is superior to that of Degussa P25 in the acidified suspension at the same pH adjusted by H2SO4.

Facile fabrication of ZnIn2S4/SnS2 3D heterostructure for efficient visible-light photocatalytic reduction of Cr（Ⅵ）

Photocatalytic method has been intensively explored for Cr(VI)reduction owing to its efficient and environmentally friendly natures.In order to obtain a high efficiency in practical application,efficient photocatalysts need to be developed.Here,ZnIn2S4/SnS2 with a three-dimensional(3D)heterostructure was prepared by a hydrothermal method and its photocatalytic performance in Cr(VI)reduction was investigated.When the mass ratio of SnS2 to ZnIn2S4 is 1:10,the ZnIn2S4/SnS2 composite exhibits the highest photocatalytic activity with 100%efficiency for Cr(VI)(50 mg/L)reduction within 70 min under visible-light irradiation,which is much higher than those of pure ZnIn2S4 and SnS2.The enhanced charge separation and the light absorption have been confirmed from the photoluminescence and UV-vis absorption spectra to be the two reasons for the increased activity towards photocatalytic Cr(VI)reduction.In addition,after three cycles of testing,no obvious degradation is observed with the 3D heterostructured ZnIn2S4/SnS2,which maintains a good photocatalytic stability.

A study on the adsorption of chromium on laterite from Guizhou Province,China

The adsorption behaviors of Cr(VI) on laterite from Guizhou Province were studied in this paper, and the adsorption mechanism was discussed as well. Results showed that different mineral compositions in the laterite would cause differences in the capacity of laterite to absorb Cr(VI). Gibbsite, iron oxide minerals and non-crystalloids are the main contributors to enhancing the capacity of laterite to absorb Cr(VI). The pH of the solution is an important factor affecting the adsorption of Cr(VI) on laterite. Acidic environment (pH=2-5) is favorable to the adsorption of Cr(VI). The amount of adsorbed Cr(VI) decreases with increasing pH of the solution. With increasing initial concentrations of Cr(VI), the amount of adsorbed Cr(VI) increases first, and then decreases. The optimal adsorption concentration of Cr(VI) on laterite is 250 μg/mL. The adsorption of Cr(VI) on laterite is a rapid process, about 80% Cr(VI) will be adsorbed within 2 hours. And the adsorption of Cr(VI) on kaolinite is a slow process.

Sorption Characteristics of Hexavalent Chromium in the Soil Based on Batch Experiment and Their Implications to the Environment

The objective of this experimental study was to determine the kinetics and equilibrium sorption of Cr(VI) in soils collected from Hengshui City of Hebei Province, China, based on batch experiments. The main concentration for this paper is on the effect of soil pH, solute concentration and ionic strength as the variable factors in the sorption of Cr(VI) in soils and the assessment of their implications to the environment. Atomic Absorption Spectrophotometer (AAS) was used for Cr(III) analysis;UV-VIS Spectrophotometer for quantification of Cr(VI) in soil samples and determination of electrical conductivity and temperature of the soil samples;and Automatic Laser Particle Size Analyzer LS230 for the determination of soil physical characteristics. Results from this study show that adsorption and reduction are major reactions accounting for removal of Cr(VI) from soil solution. It is concluded that chemical reactions such as reduction, strongly influence Cr(VI) mobility in soil. Adsorption kinetics experiments indicated that Cr(VI) removal from soil solution increases with increasing solute concentration, with decreasing pH and with decreasing ionic strength. Adsorption reactions reached equilibrium within 12 hours in batch reactors. Increasing background electrolyte concentration (KCI) decreases Cr(VI) adsorption on soil. The Cr(VI) adsorption isotherm for this soils conforms well to the Langmuir isotherm at constant pH. Two Cr(VI) adsorption parameters: the maximum sorption capacity (Qo) and Langmuir adsorption constant (KL), were determined as 1.0135 × 10-4 mol/g and 0.0622 mg/L, respectively. The reduction of Cr(VI) into less toxic Cr(III), means reduction of significant environmental problems. Finally, this study advises relevant environmental governing authorities to observeperiodic monitoring of the status of Cr(VI) in soils.

Optimization of Chromate Reduction by Whole Cells of <i>Arthrobacter</i>sp. SUK 1205 Isolated from Metalliferous Chromite Mine Environment

Arthrobacter sp. SUK 1205 isolated from metalliferous chromite mine environment of Orissa, India showed wide degree of tolerance to heavy metals including Cr(VI), variety of antibiotics and was also capable of reducing Cr(VI) during growth. Freshly grown whole cells of this bacterium were evaluated for chromate reduction under batch culture using Vogel Bonner (V. B.) broth as the base. Cells of SUK 1205 were capable of completely reducing 100 μM Cr(VI) in V. B. broth within 48 h of incubation. Reduction of chromate increased with increase in cell density which attained maximum at 1010 cells/ml, however, reverse was the phenomenon when the concentration of Cr(VI) increased gradually. Glycerol, glycine and glucose promoted chromate reduction efficiency of the cells when used as electron donors. Optimum pH and temperature were found to be 7.0 and 35°C respectively. The process of reduction was inhibited by Ni(II), Mn(II), Zn(II) and Co(II), but Cu(II) and Fe(III) was promotive in nature. On the other hand, 2, 4-dinitrophenol was found to be neither promotive nor inhibitory for the reduction process, but carbonyl cyanide-m-chloro phenyl hydrazone, sodium azide, sodium fluoride and N,N,-dicyclohexyl carboiimide were inhibitory. Cells of SUK 1205 when permeabilized with toluene, triton X-100 and tween 80 showed an enhancement of the process and thereby indicated that reduction of Cr(VI) was mainly associated with soluble component of the cells. Arthrobacter sp. SUK 1205, therefore, showed great promise for use in Cr(VI) detoxification under a wide range of environmental conditions.

Decontamination of Cr(Ⅵ) from water using sewage sludge-derived biochar: Role of environmentally persistent free radicals

Biochar is a well-known material for pollutant removal owing to its low cost and rich surface functionality. A kind of highly active substance, called environmentally persistent free radicals(EPFRs), can be produced in the preparation process of biochar, playing an important role in the removal of pollutants.In this study, sludge-derived biochars(SBC_(120) and SBC_(270)) were prepared by the hydrothermal carbonization under two temperatures(120℃ and 270℃) to investigate their removal abilities of Cr(Ⅵ). The maximum removal amounts of Cr(Ⅵ) by SBC_(120) and SBC_(270) were 16.58 and 22.93 mg·g^(-1), respectively. It was further revealed that the appearance of Cr(Ⅲ), as a result of EPFRs on sludge-derived biochar(SBC) transferred electrons to Cr(Ⅵ) in neutral solutions. That is to say, oxygen-centered(O-centered) EPFRs on SBC_(120) and carbon-centered(C-centered) EPFRs on SBC_(270) all could be used as electron donors to Cr(Ⅵ) to make it become Cr(Ⅲ). This study not only provides a theoretical basis for the mechanism of pollutants removal by sludge-derived biochar but also offers a new perspective on the direct effect of EPFRs on pollutants.

Different survival of chromium-exposed Oxya chinensis among allozyme genotypes

The goal of the present study was to compare the different survival of Oxya chinensis exposed to chromium（VI） among allozyme genotypes to gain a better understanding of the relationship between the genetic variations and environmental disturbance. This study analyzed the occurrence of genotypes in O. chinensis population exposed to Cr（VI）. O. chinensis samples were collected at Yuanping, Shanxi Province, China and used in acute toxicity tests. Specimens were assigned to Cr（VI） exposure （LDs0：291.0 mg/kg） for 24 h. The genetic composition of both dead and survived specimens was analyzed with horizontal starch gel electrophoresis in four enzymes （GPI, PGM, LDH, and ME）. The results indicated that under Cr（VI） exposure, specimens with different genotypes had various mortalities at the four loci in laboratory conditions, and there was a genetic basis for tolerance in O. chinensis during acute exposure to Cr（VI）.