Synthesis of Chromium-Doped Malayaite Pigments from Wastewater Containing Low Chromium(VI)

Abstract

A malayaite pigment was synthesized with wastewater containing low chromium (Cr)(VI) by a novel liquid-phase reaction method. The effects of the particle size of the precursor and calcination temperature on the final product are examined. The result of scanning electron microscopy shows that the obtained precursor is amorphous and the particle size is approximately 250 nm. The results of X-ray diffraction and differential scanning calorimetry show that the complete transformation temperature was approximately 1050 °C. Furthermore, the Commission International de l’Eclairage laboratory shows that the red color of as-prepared pigments is more saturated with a high a* value at 34.1. This process of malayaite pigment preparation via reuse of the Cr(VI)-containing wastewater is quite simple, economical, and energy-saving for the industry, and the products have a saturated red color. There is considerable foreground for the industrial application of this work.     

Kinetic, equilibrium isotherm and thermodynamic studies of Cr(VI) adsorption onto low-cost adsorbent developed from peanut shell activated with phosphoric acid

A particular agricultural waste, peanut shell, has been used as precursor for activated carbon production by chemical activation with H₃PO₄. Unoxidized activated carbon was prepared in nitrogen atmosphere which was then heated in air at a desired temperature to get oxidized activated carbon. The prepared carbons were characterized for surface area, surface morphology, and pore volume and utilized for the removal of Cr(VI) from aqueous solution. Batch mode experiments were conducted to study the effects of pH, contact time, particle size, adsorbent dose, initial concentration of adsorbate, and temperature on the adsorption of Cr(VI). Cr(VI) adsorption was significantly dependent on solution pH, and the optimum adsorption was observed at pH 2. Pseudo-first-order, pseudo-second-order, and intraparticle diffusion models were used to analyze the kinetic data obtained at different initial Cr(VI) concentrations. The adsorption kinetic data were described very well by the pseudo-second-order model. Equilibrium isotherm data were analyzed by the Langmuir, Freundlich, and Temkin models. The results showed that the Langmuir adsorption isotherm model fitted the data better in the temperature range studied. The adsorption capacity which was found to increase with temperature showed the endothermic nature of Cr(VI) adsorption. The thermodynamic parameters, such as Gibb’s Free energy change (ΔG°), standard enthalpy change (ΔH°), and standard entropy change (ΔS°) were evaluated.     

PBTCA稳定零价纳米铁的制备及其去除水中Cr(Ⅵ)

以2-膦酸丁烷-1,2,4三羧酸(PBTCA)为稳定剂,通过FeCl3.6H2O与NaBH4反应,利用液相还原法制备稳定纳米级零价铁颗粒(P-NZVI),并用透射电子显微镜(TEM)、扫描电子显微镜(SEM)及X射线衍射(XRD)进行表征,颗粒平均粒径为73 nm。考察了Cr(Ⅵ)溶液初始浓度、pH、NZVI投加量、温度等条件对Cr(Ⅵ)去除效果的影响,并与同等条件下不加稳定剂制备的纳米铁(N-NZVI)进行对比。结果表明:Cr(Ⅵ)的去除率随温度和纳米铁投加量增加而升高,随pH和Cr(Ⅵ)溶液初始浓度升高而降低。在相同实验条件下,P-NZVI对Cr(Ⅵ)的去除效果明显优于N-NZVI,表明改性后纳米铁在地表水原位修复领域具有较好的应用前景。     

改性蜂窝煤渣吸附Cr（VI）的动力学和热力学性能

利用碳酸钡对蜂窝煤渣进行改性,通过粉末X射线衍射光谱（XRD）和扫描电镜（SEM）对改性前后蜂窝煤渣的物质组成和形貌进行表征,研究了改性蜂窝煤渣吸附Cr（VI）的动力学和热力学性能。实验结果表明,改性蜂窝煤渣对Cr（VI）具有良好的吸附能力,吸附过程符合准二级吸附动力学模型。分别用Langmuir、Freundlich、D-R和Tempkin等4种吸附等温线模型对实验数据进行拟合,Langmuir方程拟合效果最好,25、35和45℃下的饱和吸附量分别为2．985、2．562和2．630mg／g。D—R和Tempkin模型研究表明,吸附过程属于物理吸附。热力学研究表明,改性蜂窝煤渣对Cr（VI）的吸附是一个自发的、放热过程。     

Effect of sulfate reduction activity on biological treatment of hexavalent chromium [Cr(VI)] contaminated electroplating wastewater under sulfate-rich condition

Electroplating wastewater (EW) containing heavy metals was treated by a two-stage packed-bed reactor system. The EW was highly contaminated with hexavalent chromium and other heavy metals as well as sulfate because sulfuric acid had been mainly used to polish the surface of metals to be electroplated. This acidic EW was effectively neutralized in an alkaline reactor where limestone had been packed. The neutralized wastewater together with organic wastewater from a starch-processing factory (SPW) was fed to a bioreactor packed with waste biomass. The SPW was used to supplement the electron donor in the sulfidogenic bioreactor. During the whole operation, we investigated the stoichiometry of electron to see what could be a major factor to remove Cr in the wastewater. The removal rates of sulfate and Cr(VI) were dependent on the consumption rate of organic materials in the wastewater. The stoichiometric studies also showed that about 63% of electrons from oxidation of organic materials were used to reduce sulfate. When the electrons of sulfide oxidation to elemental sulfur was at least 1.3 times higher than that of Cr(VI) reduction to Cr(III), Cr(VI) was completely removed. This result suggests that Cr(VI) reduction can be expected to take place under sulfate-rich anaerobic conditions, and sulfide produced by sulfate reducing bacteria could be used to immobilize soluble chromium through Cr(VI) reduction.     

Toxicity identification and reduction of wastewaters from a pigment manufacturing factory

In this study, major toxicants in pigment wastewaters (i.e. raw wastewater and effluent) were determined by toxicity identification evaluations (TIEs), and changes in their toxicities due to combined gamma-ray (gamma-ray) and ozone treatments were evaluated. From TIE results using Daphnia magna, Cr(VI) and o-toluidine were identified as major toxicants in the raw wastewater with concentrations of 2.47 and 25.3mg l(-1), respectively. This was confirmed by subsequent spiking and mass balance approaches. For effluent, TIE results suggested that organic anions were likely responsible for the observed toxicities. Toxicity reduction tests showed that gamma-rays with ozone treatment after coagulation was more efficient in reducing toxicities in the raw wastewater (3.9-2.0 TU) than gamma-ray treatment alone (3.9-3.1 TU). For pigment effluent, gamma-ray/O3 treatment resulted in a complete removal of the acute toxicity.     

Assessing the Cr(VI) reduction efficiency of a permeable reactive barrier using Cr isotope measurements and 2D reactive transport modeling

In Thun, Switzerland, a permeable reactive barrier (PRB) for Cr(VI) reduction by gray cast iron was installed in May 2008. The PRB is composed of a double array of vertical piles containing iron shavings and gravel. The aquifer in Thun is almost saturated with dissolved oxygen and the groundwater flow velocities are ca. 10-15m/day. Two years after PRB installation Cr(VI) concentrations still permanently exceed the Swiss threshold value for contaminated sites downstream of the barrier at selected localities. Groundwater δ(53/52)Cr(SRM979) measurements were used to track Cr(VI) reduction induced by the PRB. δ(53/52)Cr(SRM979) values of two samples downstream of the PRB showed a clear fractionation towards more positive values compared to four samples from the hotspot, which is clear evidence of Cr(VI) reduction induced by the PRB. Another downstream sample did not show a shift to more positive δ(53/52)Cr(SRM979) values. Because this latter location correlates with the highest downstream Cr(VI) concentration it is proposed that a part of the Cr(VI) plume is bypassing the barrier. Using a Rayleigh fractionation model a minimum present-day overall Cr(VI) reduction efficiency of ca. 15% was estimated. A series of 2D model simulations, including the fractionation of Cr isotopes, confirm that only a PRB bypass of parts of the Cr(VI) plume can lead to the observed values. Additionally, the simulations revealed that the proposed bypass occurs due to an insufficient permeability of the individual PRB piles. It is concluded that with this type of PRB a complete and long-lasting Cr(VI) reduction is extremely difficult to achieve for Cr(VI) contaminations located in nearly oxygen and calcium carbonate saturated aquifer in a regime of high groundwater velocities. Additional remediation action would limit the environmental impact and allow to reach target concentrations.     

Waste Fe(III)/Cr(III) hydroxide as adsorbent for the removal of Cr(VI) from aqueous solution and chromium plating industry wastewater

Fe(III)/Cr(III) hydroxide, a waste material from the fertilizer industry, has been used for the adsorption of Cr(VI) from aqueous solution, over a range of initial metal ion concentrations (5-30 mg litre(-1)), agitation times (1-180 min), adsorbent dosages (100-1200 mg per 50 ml), temperatures (24, 29 and 38 degrees C) and pH values (4.5-10). The adsorption of Cr(VI) increased with the initial concentration of Cr(VI) and with temperature. The process of uptake follows both the Langmuir and the Freundlich isotherm models. The applicability of Lagergren and empirical kinetic models has also been investigated. Almost quantitative removal of Cr(VI) at 10 mg litre(-1) in a 50-ml solution by 500 mg of adsorbent was found at an equilibrium pH of 5.6. The efficiency of chromium removal was also tested using wastewater from the chromium plating industry.     

Immobilised microbial reactor for the biotransformation of hexavalent chromium

Out of an array of bacterial strains isolated from soil contaminated with effluents from electroplating wastewater, Bacillus coagulans exhibited the maximum Cr(VI) reduction potential. The feasibility of an immobilized B. coagulans bioreactor for hexavalent chromium reduction was investigated. Experimental results demonstrated that near complete removal of Cr(VI) was achieved in the reactor with an initial Cr(VI) concentration of 26 mg/l and reactor time of 24 h. The removal efficiency in the bioreactor was significantly affected by the influent Cr(VI) concentration, the Cr(VI) loading rate, the reaction time and the amount of Cr(VI) reduced by the biomass.     

Evaluation of Acinetobacter sp. B9 for Cr (VI) resistance and detoxification with potential application in bioremediation of heavy-metals-rich industrial wastewater

Present work demonstrates Cr (VI) detoxification and resistance mechanism of a newly isolated strain (B9) of Acinetobacter sp. Bioremediation potential of the strain B9 is shown by simultaneous removal of major heavy metals including chromium from heavy-metals-rich metal finishing industrial wastewater. Strain B9 tolerate up to 350 mg L^?1 of Cr (VI) and also shows level of tolerance to Ni (II), Zn (II), Pb (II), and Cd (II). The strain was capable of reducing 67 % of initial 7.0 mg L^?1 of Cr (VI) within 24 h of incubation, while in presence of Cu ions 100 % removal of initial 7.0 and 10 mg L^?1 of Cr (VI) was observed with in 24 h. pH in the range of 6.0–8.0 and inoculum size of 2 % (v/v) were determined to be optimum for dichromate reduction. Fourier transform infrared spectroscopy and transmission electron microscopy studies suggested absorption or intracellular accumulation and that might be one of the major mechanisms behind the chromium resistance by strain B9. Scanning electron microscopy showed morphological changes in the strain due to chromium stress. Relevance of the strain for treatment of heavy-metals-rich industrial wastewater resulted in 93.7, 55.4, and 68.94 % removal of initial 30 mg L^?1 Cr (VI), 246 mg L^?1 total Cr, and 51 mg L^?1 Ni, respectively, after 144 h of treatment in a batch mode.     

Feasibility of using microalgal biomass cultured in domestic wastewater for the removal of chromium pollutants

The feasibility of obtaining and using the biomass of a microalga, Chlorella miniata, from domestic wastewater (DW) cultures for the removal of chromium(III) [Cr(III)] and chromium(VI) [Cr(VI)] was compared with that from commercial Bristol medium (BM). Results showed that Chlorella miniata cultured in DW under 16-8 hours light-dark cycle [DW(16-8)] had similar growth to that in BM [BM(16-8)], but these two biomass had different biochemical compositions, and the former one had lower carbohydrate and higher protein content. When cultured in domestic wastewater, a higher biomass was obtained under continuous illumination [DW(24-0)], and the cells had higher carbohydrate and lower protein concentrations than that of DW(16-8). The spectra of the Fourier transform infrared spectrometer revealed that the functional groups on the surface of the three kinds of biomass--DW(16-8), DW(24-0), and BM(16-8)--were comparable, except an additional peak at 1731 cm(-1) was found in the biomass cultured in domestic wastewater, which was probably the result of bacterial contamination. Although biochemical differences were found among the three kinds of microalgal biomass, similar biosorption performances to chromium pollutants were recorded, with approximately 75% Cr(III) and 100% Cr(VI) removed at equilibrium in Cr(III) and Cr(VI) experiments, respectively, when dead biomass was used as a biosorbent. Therefore, it is possible to culture Chlorella miniata in domestic wastewater and use the biomass for the removal of chromium pollutants.     

Chromium species behaviour in the activated sludge process

The purpose of this research was to compare trivalent chromium (Cr(III)) and hexavalent chromium (Cr(VI)) removal by activated sludge and to investigate whether Cr(VI) reduction and/or Cr(III) oxidation occurs in a wastewater treatment system. Chromium removal by sludge harvested from sequencing batch reactors, determined by a series of batch experiments, generally followed a Freundlich isotherm model. Almost 90% of Cr(III) was adsorbed on the suspended solids while the rest was precipitated at pH 7.0. On the contrary, removal of Cr(VI) was minor and did not exceed 15% in all experiments under the same conditions. Increase of sludge age reduces Cr(III) removal, possibly because of Cr(III) sorption on slime polymers. Moreover, the decrease of suspended solids concentration and the acclimatization of biomass to Cr(VI) reduced the removal efficiency of Cr(III). Batch experiments showed that Cr(III) cannot be oxidized to Cr(VI) by activated sludge. On the contrary, Cr(VI) reduction is possible and is affected mainly by the initial concentration of organic substrate, which acts as electron donor for Cr(VI) reduction. Initial organic substrate concentration equal to or higher than 1000 mgl(-1) chemical oxygen demand permitted the nearly complete reduction of 5 mgl(-1) Cr(VI) in a 24-h batch experiment. Moreover, higher Cr(VI) reduction rates were obtained with higher Cr(VI) initial concentrations, expressed in mg Cr(VI) g(-1) VSS, while decrease of suspended solids concentration enhanced the specific Cr(VI) reduction rate.     

Removal of Cr(VI) and humic acid by using TiO2 photocatalysis

The removal efficiencies of Cr(VI) and HA, using a TiO(2)-mediated photocatalytic process, were investigated with variations in the pH, TiO(2) dosage and Cr(VI)/HA ratio. During the photocatalytic reaction, the total removal of Cr(VI) occurred through adsorption onto TiO(2), as well as its reduction to Cr(III). However, oxidation and adsorption were identified as important removal processes for the treatment of HA. Due to the anionic type adsorption onto TiO(2) and its acid-catalyzed photocatalytic reduction, the removal of Cr(VI) decreased with increasing pH, while that of HA increased with increasing pH. The TiO(2) dosage was also an important parameter for the removal of Cr(VI). As the TiO(2) dosage was increased to 2.5 g l(-1), the removal of Cr(VI) was continuously enhanced, but decreased at dosages above 3 g l(-1) due to the increased blockage of the incident UV light used for the photocatalytic reaction. The removal of Cr(VI) was greatly enhanced when the system contained both HA and Cr(VI) compared to Cr(VI) alone. Also, the removal of HA was greatly enhanced when the system contained both HA and Cr(VI) compared to HA alone. The removal of Cr(VI) was continuously enhanced as the HA concentration gradually increased; however, no further increase was observed above 20 mg l(-1) HA due to the increased absorption of the UV light. This result supports that the photocatalytic reaction, with illuminated TiO(2), could be applied to more effectively treat wastewater containing both Cr(VI) and HA than that containing a single species only.     

青霉菌对印染废水吸附脱色及深度处理的研究

利用青霉菌P 1(Penicilliumsp )对 2种染浴废水中的染料进行吸附去除 ,研究结果表明 ,吸附处理 3h ,黑色和红色染浴废水色度基本被去除 ,去除率分别达 98 0 %和 74 5 % ,但去色处理后废水的CODCr值仍偏高。对去除色度的废水进一步用活性污泥进行深度处理 ,黑色和红色废水的CODCr去除率分别为 75 9%和 89 7%。青霉菌菌丝通过吸附作用从废水中抽提出的染料分子在有染料降解细菌L 1和L 2的降解池中脱色降解 ,菌丝吸附脱色能力得到再生。     

Investigation of Cr(VI) reduction in continuous-flow activated sludge systems

The aim of this research was to investigate hexavalent chromium, Cr(VI), reduction by activated sludge and to evaluate the use of continuous-flow activated sludge systems for the treatment of Cr(VI)-containing wastewater. Three series of experiments were conducted using two parallel lab-scale activated sludge systems. During the first experiment, one system was used as a control, while the other received Cr(VI) concentrations equal to 0.5, 1, 3 and 5mg l(-1). For all concentrations added, approximately 40% of the added Cr(VI) was removed during the activated sludge process. Determination of chromium species in the dissolved and particulate phase revealed that the removed Cr(VI) was sorbed by the activated sludge flocs mainly as trivalent chromium, Cr(III), while the residual chromium in the dissolved phase was mainly detected as Cr(VI). Activated sludge ability to reduce Cr(VI) was independent of the acclimatization of biomass to Cr(VI) and it was not affected by the toxic effect of Cr(VI) on autotrophic and heterotrophic microorganisms. During the second experiment, both systems were operated under two different hydraulic residence time (theta equal to 20 and 28h) and three different initial organic substrate concentration (COD equal to 300, 150 and 0mg l(-1)). Cr(VI) reduction was favored by an increase of theta, while it was limited by influent COD concentration. Finally, at the last experiment the effect of anoxic and anaerobic reactors on Cr(VI) reduction was investigated. It was observed that the use of an anoxic zone or an anaerobic-anoxic zone ahead of the aerobic reactor favored Cr(VI) reduction, increasing mean percentage Cr(VI) reduction to almost 80%.     

Accumulation and remobilization of aqueous chromium(VI) at iron oxide surfaces: Application of a thin-film continuous flow-through reactor

A thin-film continuous flow-through reactor was used to investigate reactions between aqueous Cr(VI) and two iron oxides, geothite and magnetite. Delayed effluent breakthrough of Cr(VI) indicated significant uptake by both oxides. Accumulation and remobilization of Cr(VI) depends on pH and the redox properties of the surface. For geothite the surface was quickly saturated and no further adsorption observed. Chromate anion (CrO₄²⁻) exhibited Langmuir-type adsorption. For magnetite, a significant slow steady-state rate of Cr(VI) uptake was observed. We propose two different mechanisms of chromium uptake: surface complexation of Cr(VI) species on geothite, and reductive precipitation of Cr(VI) at Fe(II) sites on magnetite.     

Hexavalent chromium removal by a novel Serratia proteamaculans isolated from the bank of Sebou River (Morocco)

The novel Serratia proteamaculans isolated from a chromium-contaminated site was tolerant to a concentration of 500 mg Cr(VI)/l. The optimum pH and temperature for reduction of Cr(VI) by S. proteamaculans were found to be 7.0 and 30 °C, respectively. The Cr(VI) reduction rate decreased with the increase in Cr(VI) concentration from 100 to 400 mg/l, suggesting the enzymatic chromium reduction. Resting and permeabilised cell assays provided the better evidence that chromate reduction in S. proteamaculans is enzymatic. Reduction by cell-free filtrate shows no extracellular chromate-reducing activity, revealing that this activity may be associated to membrane fraction and/or cytosolic fraction. Assays conducted with cytosolic and particulate fraction of S. proteamaculans confirmed the role of membrane-bound proteins in Cr(VI) reduction. Furthermore, chromium reduced by heat-treated cells suggests that membrane-associated chromate reductase activity of S. proteamaculans is preceded by its adsorption on the cell surface.     

Preparation of a novel iron-based biochar composite for removal of hexavalent chromium in water

The chitosan-stabilized ferrous sulfide nanoparticles were loaded on biochar to prepare a composite material FeS-CS-BC for effective removal of hexavalent chromium in water. BC and FeS-CS-BC were characterized by Brunauer–Emmett–Teller (BET), scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) analyses. Batch experiments were employed to evaluate the Cr(VI) removal performance. The experimental results showed that the removal rate of Cr(VI) by FeS-CS-BC(FeS:CS:BC?=?2:2:1) reached 98.34%, which was significantly higher than that of BC (44.58%) and FeS (79.91%). In the pH range of 2–10, the removal of Cr(VI) by FeS-CS-BC was almost independent of pH. The limitation of coexisting anions (Cl^?、SO₄^2?、NO₃^?) on Cr(VI) removal was not too obvious. The removal of Cr(VI) by FeS-CS-BC was fitted with the pseudo-second-order dynamics, which was a hybrid chemical-adsorption reaction. The X-ray photoelectron spectroscopy (XPS) analysis result showed that Cr(VI) was reduced, and the reduced Cr(VI) was fixed on the surface of the material in the form of Cr(VI)–Fe(III).

Removal of hexavalent chromium from wastewater by FeS-CS-BC composite synthesized by impregnation.

     

Sorption of Cr(VI) from dilute solutions and wastewater by live and pretreated biomass of Aspergillus flavus

Sorption of Cr(VI) was carried out from dilute solutions using live and pretreated biomass in a batch mode. Effects of agitation time, adsorbent dosage and pH were examined. The autoclaved biomass that showed maximum adsorption capacity (Q(0)=0.335 mg g(-1)) was used as an adsorbent in column studies. The optimized flow rate of 2.5 ml min(-1) and bed height 10 cm were used to determine the effect of metal ion concentration on removal of Cr(VI). Applying the BDST model to calculate the adsorption capacity (N(0)) of column, which showed 4.56 x 10(-5), 7.28 x 10(-5), 6.89 x 10(-5), 3.07 x 10(-5), 2.80 x 10(-5)mg g(-1) for 4, 8, 12, 16 and 20 mg dm(-3) of Cr(VI), respectively. Batch sorption proved to be more efficient than the column sorption and hence batch sorption was used to remove Cr(VI) from a textile dyeing industry wastewater. The phytotoxic effect of treated and untreated wastewater was studied against Zea mays. Toxicity was reduced by 50% in the treated effluent.     

Emissions of chromium (VI) from arc welding

The presence of Cr in the +6 oxidation state (Cr[VI]) is still observed in ambient air samples in California despite steps taken to reduce emissions from plating operations. One known source of emission of Cr(VI) is welding, especially with high Cr-content materials, such as stainless steels. An experimental effort was undertaken to expand and update Cr(VI) emission factors by conducting tests on four types of arc-welding operations: gas-metal arc welding (GMAW), shielded metal arc welding (SMAW), fluxcore arc welding, and pulsed GMAW. Standard American Welding Society hood results were compared with a total enclosure method that permitted isokinetic sampling for particle size-cut measurement, as well as total collection of the aerosol. The fraction of Cr(VI) emitted per unit mass of Cr electrode consumed was determined. Consistent with AP-42 data, initial results indicate that a significant fraction of the total Cr in the aerosol is in the +6 oxidation state. The fraction of Cr(VI) and total aerosol mass produced by the different arc welding methods varies with the type of welding process used. Self-shielded electrodes that do not use a shield gas, for example, SMAW, produce greater amounts of Cr(VI) per unit mass of electrode consumed. The formation of Cr(VI) from standard electrode wires used for welding mild steel was below the method detection limit after eliminating an artifact in the analytical method used.