Removal of Cr(VI) and Cr(lll) from aqueous solutions and industrial wastewaters by natural clino-pyrrhotite

This paper introduced a simple method of treating Cr(Vl)-bearing toxic wastewaters using a natural mineral: clino-pyrrhotite. Laboratory bench-scale mixing experiments were carried out in both Cr(VI)-bearing artificial solutions and industrial wastewaters under controlled conditions. The effects of solution pH, Cr(VI) concentration, mineral grain size, mineral/solution ratio, and reaction time on the Cr(VI) removal were studied. Chromium was effectively removed from the solutions and wastewaters. After the treatment, the liquid was clean enough to be discharged directly into the natural environment. The Cr(VI) removal process involved sequentially the adsorption of Cr(VI), in the form of Cr2O7(2-) or CrO4(2-), onto the mineral surface, the reduction of the adsorbed Cr(VI) to Cr(lll), catalyzed at the vacant Fe sites of the mineral, and finally the precipitation of Cr(lll) as Cr2S3, Cr2O3, and Cr(OH)3 solid phases. Conditions such as a fine mineral grain size, an excessive quantity of clino-pyrrhotite and a weak acidic media, favored the removal process. For clino-pyrrhotite with a restricted grain size, the minimum required quantity of the mineral was proportional to the total quantity of Cr(VI) to be removed. Quantitatively, one cubic meter of industrial wastewater that contained approximately 1 mmol dm(-3) of Cr(VI) and had a pH value between 1 and 10 would be effectively treated after it was in contact with 220 kg of 145 +/- 28 microm clino-pyrrhotite for an hour. Furthermore, the quantity of the final solid waste byproduct was small, and the solid residue of clino-pyrrhotite could be reused after a simple rinse with water. Compared to the previous Cr(VI)-bearing wastewater treatment schemes, this method was simple, effective, economical, and environmentally sound. It has great potential for use in industrial-scale applications.     

利用次氯酸钠去除制革污泥中的铬

本文采用次氯酸钠对制革污泥进行处理,研究了次氯酸钠去除制革污泥中铬的最佳条件。实验发现当次氯酸钠浓度为6%、液固比为22g溶液/g泥、温度60℃、反应时间为80min时,铬浸出率可达100%。     

Inhibited Cr(VI) reduction by aqueous Fe(II) under hyperalkaline conditions

This study investigated Cr(VI) reduction by dissolved Fe(II) in hyperalkaline pH conditions as found in fluid wastes associated with the U.S. nuclear weapons program. The results show that Cr(VI) reduction by Fe(II) at alkaline pH solutions proceeds very quickly. The amount of Cr(VI) removed from solution and the amount reduced increases with Fe(II):Cr(VI) ratio. However, the Cr(VI) reduction under alkaline pH condition is nonstoichiometric, probably due to Fe(II) precipitation and mixed iron(III)-chromium-(III) (oxy)hydroxides blocking Fe(II) surface sites, as well as removing Fe(II) from solution through O2 oxidation. After Cr(VI) was reduced to Cr(III), it precipitated out as mixed Fe(x)Cr1-xO3(solids) and various Fe(III) precipitates with an overall Cr:Fe ratio of 1:3; all Cr remaining in the solution phase was unreduced Cr(VI). EXAFS data showed that Cr-O and Cr-Cr distances in the precipitates equal to 1.98 and 3.01 A, respectively, consistent with the spinel-type structure as chromite.     

Removal of Pb(II) from aqueous solutions by carbons prepared from Sal wood (Shorea robusta)

In the present work, physically and chemically activated carbons are prepared using Sal wood (Shorea robusta) sawdust by thermal process and using sulfuric acid as the activation agent to remove Pb(II) from aqueous solutions. Adsorption equilibrium studies have been done at a pH of 4 and a room temperature of 30 °C. It was found that the adsorption isotherms are favorable and chemically activated carbons are better than physically activated carbon in terms of adsorption capacity. Various two-parameter adsorption isotherm models, viz. Freundlich, Langmuir, Temkin and Dubinin-Radushkevich, were used to fit the equilibrium data and it was found that the Freundlich adsorption model provided best-fit. The first-order irreversible unimolecular reaction model and the pseudo-second-order kinetic models were used to fit the kinetic data and it was found that both the models provided good fit. Kinetic and film diffusion studies show that the adsorption of lead(II) on the activated carbons tested in this work are both intra-particle and film diffusion controlled.     

Cr(VI) removal from aqueous solution by activated carbon coated with quaternized poly(4-vinylpyridine)

A composite sorbent (GAC-QPVP) was prepared by coating poly(4-vinylpyridine) onto a granular activated carbon, followed by cross-linking and quaternization processes. The sorbent was characterized by scanning electron microscopy, point of zero charge measurement, and BET analysis. Batch experiments with variable pH, ionic strength, and concentrations of Cr(VI), sorbent, and competing anions were conducted to evaluate the selective sorption of Cr(VI) from aqueous solutions. The results showed that Cr(VI) sorption rates could be described by a reversible second-order kinetics, and equilibrium uptake of Cr(VI) increased with decreasing pH, decreasing ionic strength, and increasing sorbent concentration. The estimated maximum equilibrium uptake of chromium was 53.7 mg/g at pH = 2.25, 30.7 mg/g at pH = 3.65, and 18.9 mg/g at pH = 6.03, much higher than the maximum capacity of PVP-coated silica gel, an adsorbent for Cr examined previously. When compared with the untreated granular activated carbon, sorption onto GAC-QPVP resulted in much less Cr(VI) reduction and subsequent release of Cr(III). The effect of phosphate, sulfate, and nitrate was minor on the selective sorption of Cr(VI). An ion exchange model that was linked with aqueous speciation chemistry described Cr(VI) sorption reasonably well as a function of pH, ionic strength, and Cr(VI) concentration. Model simulations suggested that sorbed Cr(VI) was partially reduced to Cr(III) on the sorbent when pH was less than 4. The presence of Cr(III) on the sorbent was confirmed by the X-ray photoelectron spectroscopic analysis. Overall, the study has demonstrated that GAC-QPVP can effectively remove Cr(VI) from aqueous solutions under a wide range of experimental conditions, without significant Cr(III) release associated with the virgin GAC treatment.     

Chromium(VI) bioremediation by probiotics

Chromium is a common mineral in the earth's crust and can be released into the environment from anthropogenic sources. Intake of hexavalent chromium (Cr(VI)) through drinking water and food causes toxic effects, leading to serious diseases, and is a commonly reported environmental problem. Microorganisms can mitigate or prevent the toxic effects caused by heavy metals in addition to having effective resistance mechanisms to prevent cell damage and bind to these metals, sequestering them from the cell surface and removing them from the body. Species of Lactobacillus, Streptococcus, Bacillus and Bifidobacterium present in the human mouth and gut and in fermented foods have the ability to bind and detoxify some of these substances. This review address the primary topics related to Cr(VI) poisoning in animals and humans and the use of probiotics as a way to mitigate or prevent the toxic effects caused by Cr(VI). Further advances in the genetic knowledge of such microorganisms may lead to discoveries which will clarify the most active microorganisms that act as bioprotectants in bodies exposed to Cr(VI) and are an affordable option for people and animals intoxicated by the oral route. © 2016 Society of Chemical Industry     

Efficient removal of Cr(VI) from aqueous solution with Fe@Fe2O3 core-shell nanowires

The batch removal of Cr(VI) from simulated wastewater with Fe@Fe2O3 core-shell nanowires (FCSNs) was investigated in this study. Itwas found that each gram of the FCSNs could remove 7.78 mg of Cr(VI) from simulated wastewater containing 8.0 mg L(-1) of Cr(VI) with an initial pH of 6.5 at room temperature. The Freundlich adsorption isotherm was applicable to describe the removal processes. Kinetics of the Cr(VI) removal was found to follow pseudo-second-order rate equation. Furthermore, the as-prepared and Cr(VI)-adsorbed FCSNs were carefully examined by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopic analysis (XPS). The characterization results suggested that the adsorbed Cr(VI) was partially reduced to Cr(lll) in Cr2O3/Cr(OH)3 on the FCSNs. The possible mechanism of removal of Cr(VI) on FCSNs was proposed, which involved the dominant Cr(VI) adsorption, followed by the partial reduction of Cr(VI) to Cr(III) (chromium(III) oxyhydroides) on the surface of FCSNs. These Fe@Fe2O3 core-shell nanowires with high specific surface area and strong magnetic property are very attractive for the removal of Cr(VI) from wastewater.     

Bacillus fusiformis对Cr(Ⅵ)的还原特性研究

探讨了Bacillus fusiformis作为处理制革中Cr(Ⅵ) 的一种新生物材料的可行性.首先在LB培养基中加入Cr(Ⅵ),检测了Bacillus fusiformis在含Cr(Ⅵ)培养基中生长后细胞内外的Cr(Ⅵ)和总铬含量;然后研究了不同Cr(Ⅵ)初始浓度、温度、Ph值、细胞生物量对Bacillus fusiformis处理Cr(Ⅵ)的影响,并在最适温度、Ph值、细胞生物量条件下,对菌株连续培养以检验其对Cr(Ⅵ)的持续还原能力;最后探究了制革中常见金属离子对Cr(Ⅵ)还原的影响.结果表明:Bacillus fusiformis处理Cr(Ⅵ)的方式可能主要为胞外还原.当初始Cr(Ⅵ)浓度不超过50 mg/L、温度32～37 ℃、Ph值7.0～8.0、细胞生物量6.7×1011 CFU/Ml时,Cr(Ⅵ)的去除率较大.在连续培养过程中,菌株具有持续的生长和还原Cr(Ⅵ)的能力.在各种金属离子的比较中得出Cu2+对Bacillus fusiformis处理Cr(Ⅵ)有较强的促进作用,Al3+、Fe3+次之,Cr3+有一定的抑制作用.研究表明,Bacillus fusiformis的还原特性可为处理制革中的Cr(Ⅵ)作参考.     

Reduction and removal of aqueous Cr(VI) by glow discharge plasma at the gas-solution interface

Aqueous chromium(VI) reduction and removal induced by glow discharge taking place at the gas-solution interface in an argon atmosphere was studied. The effect of initial pH and hydroxyl radical scavenger (ethanol) on the reduction efficiency was examined. High reduction efficiency was obtained when initial pH ≤ 2.0 or ≥ 8.0. In particular, addition of ethanol into the solution substantially increased the reduction efficiency and facilitated chromium removal from the solution in the form of sediment after discharge. The optimum pH values for Cr(VI) removal were within 6.0-7.0. Fourier transform-infrared (FTIR) spectroscopy and X-ray diffraction (XRD) analysis confirmed that the main constituent of the sediment is chromium hydroxide.     

甜菜废粕吸附性能的研究

研究了甜菜废粕吸附溶液中Cu2＋的能力,采用间歇吸附试验来评价甜菜废粕对Cu2＋的除去效率,吸附速率相对较快,在60min即可达到平衡。在间歇试验条件下,最高可达90％的去除率。废粕吸附能力与溶液pH有关,pH5．5时最大吸附Cu2＋量可达30．9mg／g。废粕添加量为8g／L足以达到最佳处理效果。     

Recovery of vanillin from aqueous solutions using macroporous adsorption resins

A simple method for recovery of dissolved vanillin from aqueous solutions by the adsorption–regeneration technique has been developed. Three macroporous adsorption resins with crosslinked-polystyrene framework were NKA-2, S-8 and H103, respectively. Static equilibrium adsorption studies were used for comparing the adsorption capacities of the three resins. The results showed that H103 resin had the best adsorption capacity because of its large and nonpolar surface areas. The effects of pH, temperature and salt concentration on the adsorption capacity of H103 were investigated. The results revealed that the resin had a maximum adsorption capacity, 416 mg/g (vanillin/resin) in acidic condition when the molecule of vanillin is neutral. Furthermore, its adsorption capacity increased with the increase of temperature and salt concentration. The mass transfer zone motion model was used for analyzing the fixed bed adsorption. H103 resin had a shorter mass transfer zone of 24.7 cm and both NKA-2 and S-8 were higher than 30 cm in the experiment conditions. More than 95.6% of adsorbed vanillin can be recovered by use of 3–5 bed volumes of absolute ethanol. The resin can be used repeatedly by simple regeneration and its adsorption capacity was almost unchangeable.     

Voltammetric detection of Cr(VI) with disposable screen-printed electrode modified with gold nanoparticles

Gold nanoparticle (Au-NP) enhanced voltammetric detection of Cr(VI) is developed for determination of trace amounts of Cr(VI) in an acetate buffer media (pH 4.6). The Au-NPs were electrodeposited onto a disposable screen printed electrode (SPE) via an electrodeposition step. It was found that the electrodeposited Au-NP has strong adsorption on Cr(VI) species, which results in an enhanced reduction current of Cr(VI). Compared with the bulk gold electrode, the reduction current of Cr(VI) was enhanced 10 times with the Au-NP-modified SPE electrode. Square wave voltammetric (SWV) measurement with the disposable Au-NP-modified SPE provides a fast, simple and sensitive detection of trace amounts of Cr(VI). The adsorption of Cr(VI) on Au-NP was characterized with voltammetry, X-ray photoelectron spectroscopy and ultraviolet spectra. The different parameters including the electrodepositing time, supporting electrolyte, and pH that govern the analytical performance of the electrode have been studied in detail and optimized. The detection limit of 5 microg L(-1) Cr (VI) was obtained under optimum experimental conditions. The performance of the sensor was successfully evaluated with river water samples spiked with Cr(VI), indicating this convenient and sensitive technique offers great promise for onsite environmental monitoring and biomonitoring of Cr(VI).     

Kinetics of Cr(VI) reduction by carbonate green rust

The kinetics of Cr(VI) reduction to Cr(III) by carbonate green rust were studied for a range of reactant concentrations and pH values. Carbonate green rust, [FeII4FeIII2(OH)12][4H2O x CO3], was synthesized by induced hydrolysis (i.e., coprecipitation) of an Fe(ll)/Fe(III) solution held at a constant pH of 8. An average specific surface area of 47 +/- 7 m2 g(-1) was measured for five separate batches of freeze-dried green rust precipitate. Heterogeneous reduction by Fe(II) associated with the carbonate green rust appears to be the dominant pathway controlling Cr(VI) loss from solution. The apparent stoichiometry of the reaction between ferrous iron associated with green rust ([Fe(II)GR]) and Cr(VI) was slightly higherthan the expected 3:1 ratio, possibly due to the presence of other oxidants, such as oxygen, protons, or interlayer carbonate ions. The rate of Cr(VI) reduction was proportional to the green rust surface area concentration, and psuedo-first-order rate coefficients (kobs) ranging from 1.2 x 10(-3) to 11.2 x 10(-3) s(-1) were determined. The effect of pH was small with a 5-fold decrease in rate with increasing pH (from 5.0 to 9.0). At low Cr(VI) concentrations (<200 microM), the rate of reaction was first order with respect to Cr(VI) concentration, whereas, at high Cr(VI) concentrations, rates appearto deviate from first-order kinetics and approach a constant value. Estimated amounts of surface Fe(II) and total Fe(II) suggest that the deviation from first-order kinetics observed at higher Cr(VI) concentrations and the 50-fold decrease in rate observed upon three sequential exposures to Cr(VI) is due to exhaustion of available Fe(II).     

Sugarcane bagasse treated with hydrous ferric oxide as a potential adsorbent for the removal of As(V) from aqueous solutions

The mechanism of As(V) removal from aqueous solutions by means of hydrated ferric oxide (HFO)-treated sugarcane bagasse (SCB-HFO) (Saccharum officinarum L.) was investigated. Effects of different parameters, such as pH value, initial arsenic concentration, adsorbent dosage, contact time and ionic strength, on the As(V) adsorption were studied. The adsorption capacity of SCB-HFO for As(V) was found to be 22.1 mg/g under optimum conditions of pH 4, contact time 3 h and temperature 22 °C. Initial As(V) concentration influenced the removal efficiency of SCB-HFO. The desorption of As(V) from the adsorbent was 17% when using 30% HCl and 85% with 1 M NaOH solution. FTIR analyses evidenced two potential binding sites associated with carboxyl and hydroxyl groups which are responsible for As(V) removal. Adsorption, surface precipitation, ion exchange and complexation can be suggested as mechanisms for the As(V) removal from the solution phase onto the surface of SCB-HFO.     

Modified barley straw as a potential biosorbent for removal of copper ions from aqueous solution

Barley straw (BS), a very low-cost material, has been utilized as a biosorbent material for the removal of copper (Cu²⁺) ions from aqueous solutions after treatment with citric acid. Barley straw was thermochemically modified with citric acid (CA–BS) for the purpose of improving the Cu²⁺ ion sorption capacity of the straw. Biosorption studies have been carried out to determine the effect of pH, adsorbent concentration, contact time, extent of modification, and adsorbate concentration on the biosorption capacity of Cu²⁺ ions by the esterified straw. The equilibrium sorption capacities of Cu²⁺ were 4.64 mg/g and 31.71 mg/g for BS and CA–BS, respectively. The optimum pH for the removal of Cu²⁺ ions by CA–BS was around pH 7.0 and the removal of Cu²⁺ ions was 88.1%. Langmuir, Freundlich, Scatchard and D–R (Dubinin–Radushkevich) isotherms have been used to characterize the observed biosorption phenomena of Cu²⁺ ions on CA–BS. The carboxyl groups on the surface of the modified barley straw were primarily responsible for the sorption of Cu²⁺ ions.     

Isolation, fractionation and characterization of melanin-like pigments from chestnut (Castanea mollissima) shells

Melanins are known as versatile biopolymers, but the utilizations are restricted by their poor solubilities. Therefore, well soluble ones or their analogs are much desired. In this article, a new procedure was developed for fractionation of the pigments isolated from chestnut (Castanea mollissima) shells, and 3 fractions (Fr. 1, Fr. 2, and Fr. 3) were obtained. The solubilities of all the fractions in waters of different pH and in common organic solvents were studied. The physicochemical properties of the fractions were characterized for the first time on the basis of combined chemical analyses and spectroscopic methods including ultraviolet-visible (UV-Vis), Fourier transform infrared (FT-IR), electron spin resonance (ESR), and solid-state (13)C nuclear magnetic resonance ((13)C-NMR). All the fractions could be bleached by NaOCl and H(2)O(2) and give a positive reaction for polyphenols, which are usually used as typical tests for allomelanins. Their UV-Vis, FT-IR, and ESR spectra resembled those of synthetic and some natural melanins. Elemental data and quantitative analyses of (13)C-NMR spectra revealed that pigment-bound proteins and polysaccharides were the most abundant in Fr. 1, while Fr. 2 was presented with the highest aromaticity. PRACTICAL APPLICATION: We provided a new, simple, and inexpensive method to fractionate the melanin-like pigments from chestnut shells. This technique can be used to produce natural melanin-like food colorants with different solubilities from chestnut shells.     

恒电流库仑法测定制革废水中铬(Ⅵ)

研究了恒电流库仑法测定制革废水中微量 Cr( )的方法及条件。在 3.5 mol/ L H2 SO4- 6 .0 mg/ m L Ce2(SO4) 3 - 0 .0 15 mol/ L Fe NH4(SO4) 2 - H3 PO4电解液中 ,加入 1- 2滴 Ag NO3 ,在快速搅拌下完成反应 ,用平衡电位法指示终点。测定 0 .5 ︼g和 1.0 - 10 0 .0 ︼g Cr( ) ,相对误差分别小于± 1.5 %和± 1.0 % ,标准偏差分别小于 0 .0 2和 0 .4。该法测定结果与比色法对照 ,结果基本一致