Preparation of MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript> from waste tannery solution and effect of sulfate,chloride, and calcium on leachability of chromium

This paper presents a study regarding the preparation of MgCr₂O₄ from waste tannery solution, and chromium leaching behavior is also investigated with varying amounts of sulfate, chloride and calcium. The phase transformation, crystallinity index and crystallite diameter were characterized using XRD, FT-IR and thermal analysis. A well-crystallized MgCr₂O₄ was successfully prepared at 1400 °C. The sintering temperature had a major impact on the formation of MgCr₂O₄ compared with sintering time. The MgCr₂O₄ phase was observed initially at 400 °C and its crystallite diameter increased with increasing temperature. The concentration of total chromium leached and Cr(VI) decreased gradually with increasing temperature. The considerable amount of Cr(VI) was found in the leachate at 300–500 °C caused by Cr(VI) intermediary products. Sulfate and chlorine could impact the transformation efficiency of chromium adversely, and chlorine has a more significant effect than sulfate. The presence of calcium disturbed the formation of MgCr₂O₄ and new chromium species (CaCrO₄) appeared, which resulted in a sharp increase in the concentration of leached Cr(VI). Incorporating Cr(III) into the MgCr₂O₄ spinel for reusable products reduced its mobility significantly. This was demonstrated to be a promising strategy for the disposal of chromium containing waste resource.     

Volatility of heavy metals during incineration of tannery sludge in the presence of chlorides and phosphoric acid.

Knowledge of the behaviour of heavy metals in the combustion process is a most important factor in selecting disposal alternatives for waste materials. Accordingly, in this work, the vaporization behaviour of highly concentrated heavy metals (Pb, Zn, Cu and Cr) in tannery sludge were investigated experimentally. The sludge was spiked with various chlorine compounds (i.e. PVC, FeCl3, CaCl2 and NaCl) and pre-treated with phosphoric acid in order to evaluate the capacity of enhancement and weakening of the volatility of the heavy metals contained in tannery sludge. The experimental results show that the vaporization percentages increased with increasing ratio of Cl/sludge and temperature, and the accelerating and increasing effect of the addition of chlorides on the vaporization percentage of heavy metals was dependent on the release capacity of chlorine radicals. The vaporization percentages of lead and zinc increased by 15-20%, whereas those of copper and chromium increased by only about 3 and 10% at 800 degrees C. However, heavy metals were not expected to be completely released in the combustion process in spite of the high ratio of Cl/sludge. Alternately, heavy metals contained in tannery sludge can be immobilized effectively by pre-treatment with phosphoric acid. When the 85% phosphoric acid accounted for 10% of dry basis of tannery sludge, the phosphate-treated sludge showed the lowest vaporization percentage of about 3-15% with formation of Ca18Cu3(PO4)14, Ca9Cr(PO4)7, Ca19Zn2(PO4)14 and PbMgP2O7 in the bottom ash.     

Optimization and Characterization of Bioactive Biocomposite Film Based on Orange Peel Incorporated with Gum Arabic Reinforced by Cr2O3 Nanoparticles

Journal of Polymers and the Environment - In this paper, the effect of adding gum arabic at levels of 0–5%, and chromium oxide nanoparticles (Cr2O3 NPs) at levels of 0–3%, were...     

Effects of the type of sintering atmosphere on the chromium leachability of thermal-treated municipal solid waste incinerator fly ash

The sintering process offers an opportunity to combine detoxification and resource recovery for the treatment of municipal solid waste (MSW) incinerator fly ash. However, the chromium (Cr) in the sintered fly ash becomes more readily leachable with increasing sintering time and temperature, thus posing severe threats to the environment and human health when the sintered ash is recycled or reused. This study investigated the enhanced leachability of fly ash containing Cr, by heating the chromium (III) oxide (Cr2O3)-spiked fly ash to 800 degrees C in atmospheres containing air, nitrogen gas (N2), and 5% H2 + 95% N2, respectively. The results indicated that trivalent chromium was converted to its soluble hexavalent form during sintering in the air atmosphere; whereas sintering in a nitrogen atmosphere significantly reduced the leachability of Cr due to lack of oxygen (O2) to oxidize. The effects of the sintering temperature on the total chromium content and the leaching concentration in the toxicity characteristic leaching procedure (TCLP) extract are also discussed.     

A study of heavy metals and their fate in the composting of tannery sludge

Tannery waste is categorized as toxic and hazardous in Malaysia due to its high content of Cr (in excess of 500 mg/kg) and other heavy metals. Heavy metals, when in high enough concentrations, have the potential to be both phytotoxic and zootoxic. Heavy metals are found as contaminants in tannery sludge. This investigation aimed to identify the fate of chromium, cadmium, copper, lead, and zinc concentrations in tannery sludge throughout a 50-day composting cycle. The results of this study showed a general increase in the removal of Cr, Cd, Pb, and to a much smaller extent Zn and Cu, manifested by a decrease in their overall concentrations within the solid fraction of the final product (the decreases were likely the result of leaching). Furthermore, in using a sequential extraction method for sludge composting at different phases of treatment, a large proportion of the heavy metals were found to be associated to the residual fraction (70-80%) and fractions more resistant to extraction, X-NaOH, X-EDTA, X-HNO3 (12-29%). Less than 2% of the metals were bound to bioavailable fractions X-(KNO3+H2O).     

Utilisation of Supernatants of Pure Cultures of Streptomyces thermocarboxydus NH50 to Reduce Chromium Toxicity and Mobility in Contaminated Soils

Chromium is a heavy metal used in various industrial sectors. Improper handling and storage of chromium-laden effluents or wastes can lead to the pollution of the environment. The most toxic form is the more mobile one: hexavalent chromium Cr(VI). The reduction of Cr(VI) results in the immobilisation of chromium into its less toxic trivalent form Cr(III). This phenomenon may prevent the contamination of groundwater when the soil in the vadose zone is contaminated. Many bacteria have been isolated from contaminated soils and described to reduce Cr(VI) into Cr(III). A new Cr(VI)-reducing strain, identified as a Streptomyces thermocarboxydus,has been isolated and studied in our laboratories for its ability to reduce Cr(VI). This aerobic bacterium, in contrast to other genera described which mediate reduction via enzymes, produces reducing agents into the culture supernatants. Cr(VI) reduction by these substances is accelerated by the presence of small concentration of cupric ions (Cu²⁺). The reducing agent(s) can be easily recovered from the bacterial cultures and used as cell-free solution to treat contaminated soils by an in situ or ex situ processes.     

Sequential solid phase extraction protocol followed by liquid chromatography–atmospheric pressure chemical ionization–mass spectrometry for the trace determination of non ionic polyethoxylated surfactants in tannery wastewaters

Automated solid-phase extraction (SPE) with C18 and styrene–divinylbenzene cartridges in series was used for the preconcentration of non ionic polyethoxylated surfactants in tannery wastewater. Fractionated extracts were analyzed by LC–MS using Atmospheric Pressure Chemical Ionization (APCl) in the Positive and Negative Ion modes. Recoveries for nonionic surfactants were approximately of 72, 90 and 80% for polyethylene glycols, nonylphenol and alcohol ethoxylates in the polar, aromatic and medium polarity fractions, respectively. Data acquisition in the selected ion monitoring mode afforded limits of quantification from 0.1 to 0.8 μg/l for tridecylic polyethoxylated alcohol and polyethoxylated glycol, respectively, in the complex tannery wastewaters. The tannery effluents investigated contained between 0.03 to 3.0 mg/l of polyethylene glycol and nonylphenol polyethoxylate, respectively. ©     

Industrial wastewater analysis: a toxicity-directed approach

Methods of toxicity-directed analysis have been developed for the characterization and identification of toxic organic constituents in industrial wastewater. Sequential solid-phase extraction is followed by high-performance liquid chromatography (HPLC) fractionation or by automated multiple development thin-layer chromatography fractionation (AMD–TLC) of the toxic extracts. Toxic fractions were finally analyzed by gas chromatography–mass spectroscopy (GC–MS). Toxicity was detected before each of the analytical steps by the bioluminescence inhibition of Vibrio fischeri, which was performed on microtiter plates and on the developed TLC plates. While sequential extraction broadens the polarity range of the procedure, the new variants of the luminescence test make the method very versatile and fast. The potential of this kind of toxicity-directed analysis with respect to resolution and polarity of analytes is discussed and applications to partial effluents of a tannery, to molasses wastewater and a spent dyeing bath are presented. A variety of benzothiazoles and more polar organics were identified as major toxic compounds in tannery effluents. It is shown that the procedures are well suited to detect individual toxic components in complex industrial wastewaters. The use of LC-MS is proposed to extend the polarity range of the final identification step. ©     

Uptake of chromium by Aspergillus foetidus

Aspergillus foetidus has the ability to take up chromium during the stationary phase of growth and under growth-nonsupportive conditions. We observed a 97% decrease in hexavalent chromium (initial concentration 5 µg/g) at the end of 92 h of growth, which may be due to its reduction to Cr (III) and/or complexation with organic compounds released due to the metabolic activity of the fungus. Replacement culture studies under growth-nonsupportive conditions revealed that the maximum uptake of Cr (VI) at pH 7.0 is 2 mg/g of dry biomass. At low or high pH values, Cr (VI) uptake is significantly reduced. In addition, the initial rate of total chromium uptake is also enhanced by higher biomass concentrations and the presence of glucose. The results obtained through this investigation indicate the possibility of treating waste effluents containing hexavalent chromium using Aspergillus foetidus.     

Electrokinetic remediation of heavy metal-contaminated soils under reducing environments

This paper describes the migration of hexavalent chromium, Cr(VI), nickel, Ni(II), and cadmium, Cd(II), in clayey soils that contain different reducing agents under an induced electric potential. Bench-scale electrokinetic experiments were conducted using two different clays, kaolin and glacial till, both with and without a reducing agent. The reducing agent used was either humic acid, ferrous iron, or sulfide, in a concentration of 1000 mg/kg. These soils were then spiked with Cr(VI), Ni(II), and Cd(II) in concentrations of 1000, 500 and 250 mg/kg, respectively, and tested under an induced electric potential of 1 VDC/cm for a duration of over 200 h. The reduction of chromium from Cr(VI) to Cr(III) occurred prior to electrokinetic treatment. The extent of this Cr(VI) reduction was found to be dependent on the type and amount of reducing agents present in the soil. The maximum reduction occurred in the presence of sulfides, while the minimum reduction occurred in the presence of humic acid. The concentration profiles in both soils following electrokinetic treatment showed that Cr(VI) migration was retarded significantly in the presence of sulfides due both to the reduction of Cr(VI) to Cr(III) as well as an increase in soil pH. This low migration of chromium is attributed to: (1) migration of Cr(VI) and the reduced Cr(III) fraction in opposite directions, (2) low Cr(III) migration due to adsorption and precipitation in high pH regions near the cathode in kaolin and throughout the glacial till, and (3) low Cr(VI) migration due to adsorption in low pH regions near the anode in both soils. Ni(II) and Cd(II) migrated towards the cathode in kaolin; however, the migration was significantly retarded in the presence of sulfides due to increased pH through most of the soil. Initial high pH conditions within the glacial till resulted in Ni(II) and Cd(II) precipitation, so the effects of reducing agenets were inconsequential. Overall, this study demonstrated that the reducing agents, particularly sulfides, in soils may affect redox chemistry and soil pH, ultimately affecting the electrokinetic remediation process.     

Optimum Dose Of Lime And Fly Ash For Treatment Of Hexavalent Chromium–Contaminated Soil

The presence of hexavalent chromium, Cr(VI), in soil is an environmental concern due to its effect on human health. The concern arises from the leaching and the seepage of Cr(VI) from soil to groundwater. In this paper, a stabilization technology to prevent this problem was simulated on an artificial soil contaminated with hexavalent chromium. The process is a physico-chemical treatment in which the toxic pollutant is physically entrapped within a solid matrix formed by the pozzolanic reactions of lime and fly ash to reduce its leachability and, therefore, its toxicity. This paper presents the optimum ratio of fly ash and lime in order to stabilize artificial soils contaminated with 0.4 wt.% of Cr (VI) in a brief term process. The degree of chromium released from the soil was evaluated using a modified Toxicity Characteristic Leaching Procedure (TCLP) by US Environmental Protection Agency (EPA). Overall, experimental results showed reduced leachability of total and hexavalent chromium from soils treated with both fly ash and quicklime, and that leachability reduction was more effective with increasing amount of fly ash and quicklime. Stabilization percentages between 97.3% and 99.7% of the initial chromium content were achieved, with Cr(VI) concentration in the TCLP leachates below the US EPA limit for chromium of 5 mg/l. Adequate treatment was obtained after 1 day of curing with just 25% fly ash and 10% quicklime.     

Using Chitosan as a Coagulant in Recovery of Organic Matters from the Mash and Lauter Wastewater of Brewery

Chitosan is a natural biopolymer which can be used to replace aluminum salts and chemical polymers as a coagulant to avoid the human health problems caused by the residual of aluminum and chemical polymers in water. Chitin is a major component in shrimp and crab shells, and chitosan can be produced from chitin via a deacetylated process. Since the biodegradation of chitin is very slow, large amount of discards from the processing of crustaceans has become a major concern in seafood industry. Therefore, more works are need to find the possible applications of chitin, chitosan and their derivatives. This research used chitosan as a coagulant to recover wheat dregs in the wastewater from washing the mash and the lauter unit in a brewery, and regards this study as an example to understand the influences of the characters of the wastewater on the treatment plant of brewery. The result shows that the␣wastewater from the mash and the lauter units can have the best treatment efficiency at the coagulant dosage of 120 mg/L in the original pH 4.5. Increasing the solution pH decreased the turbidity removal efficiency. The dominant mechanisms for chitosan to remove colloids in the␣wastewater are charge bridging and neutralization, and the later becomes less significant in␣the high pH. The coagulant of chitosan removed most of the colloidal form organic matter in the wastewater, but it has only little effect on the removal of dissolving organic matter. Chitosan is a natural material, after coagulation the sludge from the mash and lauter wastewater can serve directly as an animal husbandry fodder after been dehydrated. Therefore, the loading to wastewater treatment plant and the cost of treatment could be reduced.     

Thermal valorization of footwear leather wastes in bubbling fluidized bed combustion

Transformation of hide (animal skins) into leather is a complicated process during which significant amounts of wastes are generated. Footwear is the sector that consumes the major part of leather (60%). Logically, this industry is producing the largest quantity of leather wastes. The objective of this work was to demonstrate the technical feasibility of fluidized bed technology to recover the energy from burning footwear leather wastes. Considering the characteristics of leather waste, especially the heating value (12.5-21 MJ/kg), it can be considered a fairly good fuel. Moreover, leather waste has suitable characteristics for combustion, e.g., high volatile matter (76.5%) and low ash content (5.2%). Two factors deserve special attention: N3O and NOx emissions as a consequence of its unusual high nitrogen content (14.1%) and the chromium speciation because chromium is the main element of ash (3.2%) due to its use in leather tanning. A series of experiments has been carried out in a 0.1 MWt bubbling fluidized bed pilot plant. The combustion efficiency, flue gas composition and chromium speciation were investigated. Despite having high nitrogen content, a low conversion rate of fuel-N to NOx and N2O was attained. Chromium was concentrated in the solid streams and it was consistently found as Cr(III+); no presence of Cr(VI+) was detected.     

Vitrification as an alternative to landfilling of tannery sewage sludge

Due to high content of heavy metals such as chromium, tannery sewage sludge is a material which is difficult to be biologically treated as it is in the case of organic waste. Consequently, a common practice in managing tannery sewage sludge is landfilling. This poses a potential threat to both soil and water environments and it additionally generates costs of construction of landfills that meet specific environment protection requirements. Vitrification of this kind of sewage sludge with the addition of mineral wastes can represent an alternative to landfilling.The aim of this study was to investigate the possibility of obtaining an environmentally safe product by means of vitrification of tannery sewage sludge from a flotation wastewater treatment process and chemical precipitation in order to address the upcoming issue of dealing with sewage sludge from the tannery industry which will be prohibited to be landfilled in Poland after 2016. The focus was set on determining mixtures of tannery sewage sludge with additives which would result in the lowest possible heavy metal leaching levels and highest hardness rating of the products obtained from their vitrification.The plasma vitrification process was carried out for mixtures with various amounts of additives depending on the type of sewage sludge used. Only the materials of waste character were used as additives.One finding of the study was an optimum content of mineral additives in vitrified mixture of 30% v/v waste molding sands with 20% v/v carbonate flotation waste from the zinc and lead industry for the formulations with flotation sewage sludge, and 45% v/v and 5% v/v, respectively, for precipitation sewage sludge. These combinations allowed for obtaining products with negligible heavy metal leaching levels and hardness similar to commercial glass, which suggests they could be potentially used as construction aggregate substitutes. Incineration of sewage sludge before the vitrification process lead to increased hardness of the vitrificates and reduced leaching of some heavy metals.     

Optimizing Cr(VI) adsorption on activated carbon produced from heavy oil fly ash

In order to explore the beneficial utilization of heavy oil fly ash (HOFA) generated in the power plants, the present study is intended to optimize the chromium(VI) [Cr(VI)] adsorption on activated carbon produced from HOFA. The raw HOFA obtained from a power plant was washed by nitric/hydrochloric acid and activated at 800 °C with a holding time of 60 min to produce fly ash activated carbon (FAC). Phosphoric acid was used as a chemical agent to improve the surface characteristics of the HOFA during the activation process. Batch adsorption experiments were employed to evaluate the effects of different parameters such as initial Cr(VI) concentration, pH, and FAC dose on the removal of Cr(VI) from aqueous solution. A total of 17 adsorption experimental runs were carried out employing the detailed conditions followed the response surface methodology based on the Box–Behnken design. The results indicate that developed FAC has the potential for removing Cr(VI) from wastewater. Under the test conditions, a maximum of 91.51 % Cr(VI) removal efficiency was achieved.     

铁矿石烧结烟气脱硫灰处理含铬废水

在分析铁矿石烧结烟气脱硫灰成分的基础上,利用脱硫灰中的亚硫酸盐还原废水中的Cr(Ⅵ),再加碱中和,通过沉淀去除铬。在初始废水pH 1.0、脱硫灰加入量0.06 g/mg(以Cr(Ⅵ)计)、振荡转速160 r/min、振荡时间25 min、中和pH 7.5的最佳工艺条件下处理模拟含铬废水,Cr(Ⅵ)质量浓度由10.00 mg/L降至0.18 mg/L,去除率达98.2%。最佳工艺条件下处理3种实际含铬废水,处理后出水的Cr(Ⅵ)和总铬的质量浓度及pH均满足GB 8978—1996《污水综合排放标准》。实现了对脱硫灰的综合利用、化害为利和以废治废的目标。     

Effect of microbial activity on the mobility of chromium in soils

The effect of microbial activity on the chemical state of chromium, in a contaminated soil located in the Rh?ne-Alpes region (France), has been investigated. This soil contained 4,700 mg kg(-1) Cr, with about 40% present in the soluble hexavalent form. Indigenous microbial activity was found to significantly reduce Cr(VI) to the less mobile form (III) when the soil was incubated at 30 degrees C in an aqueous medium containing glucose and nutrients. A Cr(VI)-reducing strain of Streptomyces thermocarboxydus was isolated from the contaminated soil. The strain was found to metabolize Cr(VI) in a similar manner as an exogenous inoculum of Pseudomonas fluorescens LB300, and to precipitate chromium as a Cr oxyhydroxide with a gammaCrOOH-like local structure. The Cr(VI)-reducing activity of S. thermocarboxydus was induced, or significantly accelerated, by the aggregation of bacterial cells or their adhesion to suspended solid particles, and was stimulated in pure culture by glycerol and chromate.     

Fabrication of Polypyrrole/Chitosan Nanocomposite Aerogel Monolith for Removal of Cr(VI)

Three-dimensional polypyrrole/chitosan nanocomposite monoliths are fabricated by polymerization of pyrrole in chitosan aqueous solution. The static polymerization of pyrrole monomer and the cross-linking of chitosan by glutaraldehyde occur simultaneously, resulting in the self-assembly of polypyrrole/chitosan nanocomposite aerogel monolith. The addition of methyl orange and glutaraldehyde and the static reaction play key roles in the formation of the self-standing aerogel monolith. The as-prepared monolith with larger specific surface area exhibits much better adsorption capability for Cr(VI) removal in comparison with that prepared without the addition of glutaraldehyde. The adsorption process and adsorption isotherms are found to well follow the pseudo-second-order and Langmuir models, respectively. Furthermore, this polypyrrole/chitosan nanocomposite monolith is stable and recyclable. About 73.5% of the initial adsorption capability is kept after eight adsorption–desorption cycles. The polypyrrole/chitosan nanocomposite monolith can be a promising candidate for the efficient removal of Cr(VI).     

铬渣资源化处理的零排放工艺

采用氧化—还原法对某钢厂的粗铬渣进行提纯回收，对各项工艺参数进行了优化，探讨了铬渣零排放处理工艺的可行性。实验结果表明：在氧化温度80 ℃、氧化时间1.5 h、双氧水加入量2.35 mL/g（以铬渣计），还原时间15 min、还原pH 1.5、NaHSO₃加入量0.445 g/g（以铬渣计），沉淀pH 8.0，煅烧温度1 050 ℃、煅烧时间1 h的条件下，所得废渣的w（Cr）为1.29%，回收铬绿产品的w（Cr₂O₃）为97.20%，铬回收率为94.40%;处理后废水的ρ（总铬）约为0.06 mg/L，低于GB 13456—2012《钢铁工业水污染物排放标准》中规定的1.50 mg/L，既可作为循环用水，也可排放;处理后废渣中含大量硅元素，可作为生产水泥发泡节能砖或砌块的原料;整个回收过程清洁无污染，零排放，且具备一定的盈利空间。     

A New Montmorillonite-Based Porous Composites: Effectively Removal of Cr(III)-Organic Complexes in Tannery Wastewater

Journal of Polymers and the Environment - Montmorillonite-based porous adsorbent prepared by gel casting method was used to adsorb Cr(III)-organic complexes in tanning wastewater,together with the...