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.     

Simultaneous decontamination of hexavalent chromium and methyl tert-butyl ether by UV/TiO2 process

Hexavalent chromium and methyl tert-butyl ether (MTBE) are two important environmental pollutants. Simultaneous decontamination of Cr(VI) and MTBE was studied by UV/TiO2 process. The influences of pH and the concentrations of pollutants on the kinetics of the photocatalytic reactions were evaluated. Dark adsorption tests showed that the acidic pH favored the adsorption of Cr(VI) while neutral pH favored the adsorption of MTBE. Under UV irradiation, Cr(VI) reduction was observed in Cr(VI)/TiO2 system, and MTBE oxidation was observed in MTBE/TiO2 system. The system containing Cr(VI) and MTBE by UV/TiO2 process demonstrated the synergistic effect between oxidation of MTBE and reduction of Cr(VI). The results demonstrated that two pollutants Cr(VI) and MTBE could be eliminated simultaneously by UV/TiO2 process. tert-Butyl formate, tert-butyl alcohol and acetone were identified as primary degradation products of MTBE by gas chromatography-mass spectrometry in the degradation of MTBE by UV/TiO2 process.     

Transportation and distribution of chromium in the anaerobic sludge treating the chromium-containing wastewater

The chromium distribution and transportation in the anaerobic activated sludge was investigated using a sequential extraction method. The results showed that Cr(VI) in aqueous solution was reduced by the metabolic product of SRB and form indissoluble Cr(OH)₃ in a solid phase. More than 99% of Cr(III) in the sludge was in a stable residual form (RES) of bio-reduction. The Cr(VI) was mainly present in RES and organic form (OR). With increasing Cr(VI) concentration, Cr(VI) was transferred from RES into OR and even exchangeable form (EXCH). Meanwhile, sulphate and co-existing metal ions affected the occurrence form of Cr(VI).     

Oxidation-reduction potential changes in aeration tanks and microprofiles of activated sludge floc in medium- and low-strength wastewaters.

Real-time control of aeration tank operation is key to high-efficiency pollutant removal and energy savings. One of the aims of this study was to examine the potential for using redox potential (oxidation-reduction potential [ORP]) to indicate wastewater quality online in aeration tanks treating medium (chemical oxygen demand [COD] of 70 to 150 mg/L) and low (COD of 15 to 30 mg/L) pollutant-concentration wastewaters. The field-scale data provide a good relationship between ORP values and nutrient removal along the length of the aeration tanks. The ORP values increased dramatically as organic matter was removed along the aeration tanks, indicating the improvement of the bulk liquor redox status. Dissolved oxygen higher than 1.0 mg/L was necessary for good biodegradation and improvement of the liquid redox status. Nitrification occurred at higher ORP values (380 to 420 mV) than was the case for organic substrate oxidation (250 to 300 mV). The microprofiles obtained from microelectrode measurements substantiate the heterogeneity of the microbial processes inside activated sludge flocs. Because of microbial oxygen utilization, the aerobic region in the activated sludge floc was limited to the top layer (0.1 to 0.2 mm) of the activated sludge aggregate present in medium-strength wastewater, with an anoxic zone dominating inside the flocs. When dissolved oxygen in the bulk water was higher than 4.0 mg/L, the anoxic zone inside the floc disappeared. At low wastewater pollutant concentrations, the ORP and dissolved oxygen inside the activated sludge aggregates were higher than those from medium-strength wastewater. The prospect of using ORP as an online control approach for aeration tank operation and the potential reasons for activated sludge floc size varying with pollutant strengths are also discussed.     

A study on the Cr(VI) removal from aqueous solutions by steel wool

The reduction of Cr(VI) by steel wool and the precipitation of reduced chromium by CaCO(3) powder and NaOH solution were investigated in continuous and batch systems, respectively. The effects of acid and initial Cr(VI) concentrations, volumetric rate and temperature of solution on Cr(VI) reduction were studied. The results showed that the reduction of Cr(VI), to a large extent, depended on, and increased with, acid concentration. The Cr(III) and iron ions in the reduced solution were completely precipitated by using NaOH solution at appropriate alkaline conditions. It was concluded that CaCO(3) powder could be used as a cheap precipitant for Cr(III) ions. But the iron ions in the reduced solution could not be fully removed by using this precipitant.     

Investigation of triclosan fate and toxicity in continuous-flow activated sludge systems

The purpose of this research was to study the fate and toxicity of triclosan (TCS) in activated sludge systems and to investigate the role of biodegradation and sorption on its removal. Two continuous-flow activated sludge systems were used; one system was used as a control, while the other received TCS concentrations equal to 0.5 and 2mgl(-1). At the end of the experiment, 1mgl(-1) TCS was added in the control system to investigate TCS behaviour and effects on non-acclimatized biomass. For all concentrations tested, more than 90% of the added TCS was removed during the activated sludge process. Determination of TCS in the dissolved and particulate phase and calculation of its mass flux revealed that TCS was mainly biodegraded. Activated sludge ability to biodegrade TCS depended on biomass acclimatization and resulted in a mean biodegradation of 97%. Experiments with batch and continuous-flow systems revealed that TCS is rapidly sorbed on the suspended solids and afterwards, direct biodegradation of sorbed TCS is performed. Regarding TCS effects on activated sludge process, addition of 0.5mgl(-1) TCS on non-acclimatized biomass initially deteriorated ammonia removal and nitrification capacity. After acclimatization of biomass, nitrification was fully recovered and further increase of TCS to 2mgl(-1) did not affect the performance of activated sludge system. The effect of TCS on organic substrate removal was minor for concentrations up to 2mgl(-1), indicating that heterotrophic microorganisms are less sensitive to TCS than nitrifiers.     

铬离子对SBR工艺活性污泥毒性作用研究

针对重金属铬离子对SBR工艺系统中活性污泥的毒性作用,通过检测不同初始污泥容积指数(SVI)下SBR工艺活性污泥在不同铬负荷下的COD值、挥发性污泥浓度以及受铬离子影响的污泥容积指数(SVI),研究重金属铬离子对活性污泥的毒性作用以及对SBR工艺系统处理污水的影响。研究表明,重金属铬离子会导致SBR工艺系统出水COD升高;将铬离子对活性污泥的毒性作用按照挥发性污泥(MLVSS)铬负荷可划分为耐受范围、非耐受范围、细胞失活范围以及细胞分解范围。耐受范围铬负荷低于约30 mg Cr3+/gMLVSS,此范围内铬离子对于活性污泥的毒性作用不大,不致于导致系统出水水质变差;非耐受范围铬负荷在约30~65 mg Cr3+/g MLVSS,在铬离子作用下系统出水COD值明显高于对照系统;细胞失活范围铬负荷在约70~100 mg Cr3+/gMLVSS范围内,SVI大幅下降,微生物部份死亡和失活,出水COD尽管有一些下降,但与进水COD相比差不了多少;细胞分解范围铬负荷在约100 mg Cr3+/gMLVSS以上,微生物大量死亡,部分死亡细胞分解,系统出水COD值因微生物的死亡分解而超出进水COD值,受铬离子影响的系统SVI值大幅度降低。     

好氧/缺氧消化降解污泥特征分析

为考察好氧/缺氧消化过程中污泥降解的特征,利用2个反应器进行对比试验,研究好氧/缺氧和好氧消化2个过程中VS的去除,pH和碱度变化,消化上清液中COD和氮元素变化等情况。试验结果表明:好氧/缺氧消化能够满足污泥稳定的要求,在常温条件下,消化16 d VS去除率即可达到38.2%,同时比好氧消化节约曝气能耗。好氧/缺氧消化对污泥中总氮的去除率高于传统的好氧消化,达到了36.4%,而且能够降低消化污泥上清液中的氨氮和硝态氮浓度。     

Effect of amorphous silica and silica sand on removal of chromium(VI) by zero-valent iron

The effect of two surfaces (amorphous silica and silica sand) on the reduction of chromium(VI) by zero-valent iron (Fe(0)) was investigated using batch reactors. The amendment of both surfaces significantly increased the rate and extent of Cr(VI) removal. The rate enhancement by amended surfaces is presumed to result from scavenging of Fe(0)-Cr(VI) reaction products by the provided surfaces, which minimized surface deactivation of Fe(0). The rate enhancing effect was greater for silica compared to sand, and the difference is attributed to silica's higher surface area, greater affinity for reaction products and pH buffering effect. For a given mass of Fe(0), the reactivity and longevity of Fe(0) to treat Cr(VI) increased with increasing dose of silica. Elemental analyses of the reacted iron and silica revealed that chromium removed from the solution was associated with both surfaces, with its mass distribution being approximately 1:1 per mass of iron and silica. The overall result suggests reductive precipitation was a predominant Cr(VI) removal pathway, which involves initial reduction of Cr(VI) to Cr(III), followed by formation of Cr(III)/Fe(III) hydroxides precipitates.     

Reliable evidences that the removal mechanism of hexavalent chromium by natural biomaterials is adsorption-coupled reduction

For the last few decades, over 200 papers have been published in the Cr(VI) biosorption research field. Most early studies have claimed that Cr(VI) was removed from aqueous phase through an anionic adsorption, but this approach has been lost old original position. It has been newly explained that these findings were misinterpreted due to errors in measuring the concentrations of different chromium species in the aqueous phase, insufficient contact time required for equilibrium and the lack of information about the oxidation state of the chromium bound to biomaterials. Although 'adsorption-coupled reduction' is now widely accepted as the mechanism of Cr(VI) biosorption by natural biomaterials, a number of researchers still believe that Cr(VI) is removed by anionic adsorption onto the biomaterials. Therefore, the objective of this study was to show reliable evidences that the removal mechanism of Cr(VI) by natural biomaterials is 'adsorption-coupled reduction'. Sixteen natural biomaterials were used to study the Cr(VI) biosorption. Not only Cr(VI) but also total Cr in the aqueous phase were analyzed. X-ray photoelectron spectroscope was also used to verify the oxidation state of the chromium bound to the biomaterials. Finally, the removal behavior of Cr(VI) by each biomaterial was described by a kinetic model based on a redox reaction.     

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.     

Biodegradation of triclosan and formation of methyl-triclosan in activated sludge under aerobic conditions

Triclosan is an antimicrobial agent which is widely used in household and personal care products. Widespread use of this compound has led to the elevated concentrations of triclosan in wastewater, wastewater treatment plants (WWTPs) and receiving waters. Removal of triclosan and formation of triclosan-methyl was investigated in activated sludge from a standard activated sludge WWTP equipped with enhanced biological phosphorus removal. The removal was found to occur mainly under aerobic conditions while under anoxic (nitrate reducing) and anaerobic conditions rather low removal rates were determined. In a laboratory-scale activated sludge reactor 75% of the triclosan was removed under aerobic conditions within 150 h, while no removal was observed under anaerobic or anoxic conditions. One percent of the triclosan was converted to triclosan-methyl under aerobic conditions, less under anoxic (nitrate reducing) and none under anaerobic conditions.     

生物铁泥的Fe（Ⅲ）还原能力及影响因素

以生物铁泥和普通活性污泥为对象,在不同碳源及兼氧/厌氧条件下采用实验室恒温培养的方法考察了不同活性污泥的Fe（Ⅲ）还原性能。研究结果表明,不同活性污泥Fe（Ⅲ）还原能力相差较大,生物铁泥的Fe（Ⅲ）还原性能明显优于普通活性污泥,在兼性厌氧与严格厌氧条件下,分别是普通活性污泥的1.87倍和1.76倍;碳源对生物铁泥的Fe（Ⅲ）还原影响较小,而对普通活性污泥的Fe（Ⅲ）还原过程呈现出较明显的负影响;在实验控制的兼氧/厌氧条件下,2种活性污泥厌氧条件下Fe（Ⅲ）还原能力均大于兼氧条件。为活性污泥Fe（Ⅲ）还原过程的工程实际应用提供了理论依据。     

Effect of N-hydroxyethyl-ethylenediamine-triacetic acid (HEDTA) on Cr(VI) reduction by Fe(II)

The complexation of Fe(II) with organic ligand results in the decrease of redox potential, and enhances the reduction ability of Fe(II). An important example is the use of Fe(II)-organic complexes to accelerate Cr(VI) reduction. Dissolved O(2) and light can potentially affect Cr(VI) reduction; however, these two factors have not been adequately evaluated. A batch technique was used to investigate the Cr(VI) reduction as influenced by the light and dissolved O(2) using N-hydroxyethyl-ethylenediamine-triacetic acid (HEDTA) and Fe(II) solutions. The oxidation of Fe(II) by dissolved O(2) was rapid in the presence of HEDTA at low pH; nonetheless, the oxidation proceeded slowly when HEDTA was absent. Although Cr(VI) could be reduced by free Fe(II) at low pH, the reaction was considerably slower than that of systems involving HEDTA. The enhancement of Cr(VI) reduction by Fe(II) in the presence of high concentrations of HEDTA was achieved as a result of two processes. First, HEDTA acted as a ligand for expediting electron transfer between Fe(II) and Cr(VI). Secondly, HEDTA served as a reductant for Cr(VI) under illumination.     

Biogeochemical influence on transport of chromium in manganese sediments: experimental and modeling approaches

Hexavalent chromium (Cr(VI)) was reduced to immobile and nontoxic Cr(III) by a dissimilatory metal reducing bacteria, Shewanella alga Simidu (BrY-MT) ATCC 55627. A series of kinetic batch and dynamic column experiments were conducted to provide an understanding of Cr(VI) reduction by the facultative anaerobe BrY-MT. Reduction of Cr(VI) was rapid (within 1 h) in columns packed with quartz sand and bacteria, whereas Cr(VI) reduction by BrY-MT was delayed (57 h) in the presence of beta-MnO2-coated sand. A mathematical model was developed and evaluated against data obtained from column experiments. The model takes into account (1) advective-dispersive transport of Cr(III), Cr(VI), lactate, and protein (mobile and immobile bacteria); (2) first-order kinetic adsorption of Cr(III) and lactate; (3) conversion of solid phase beta-MnO2 to solid phase MnOOH due to oxidation of Cr(III); (4) dual-Monod kinetics, where Cr(VI) is the electron acceptor and lactate is the electron donor. The breakthrough data for Cr(III), Cr(VI), lactate, and protein (mobile and immobile bacteria) were fitted simultaneously. The breakthrough data are well described by the mathematical model that considers the above processes. This result demonstrates the ability of the coupled hydrobiogeochemical model to simulate chromium transport in complex reactive systems.     

Chromium accumulation by the hyperaccumulator plant Leersia hexandra Swartz

Leersia hexandra Swartz (Gramineae), which occurs in Southern China, has been found to be a new chromium hyperaccumulator by means of field survey and pot-culture experiment. The field survey showed that this species had an extraordinary accumulation capacity for chromium. The maximum Cr concentration in the dry leaf matter was 2978 mg kg(-1) on the side of a pond near an electroplating factory. The average concentration of chromium in the leaves was 18.86 times as that in the pond sediment, and 297.41 times as that in the pond water. Under conditions of the nutrient solution culture, it was found that L. hexandra had a high tolerance and accumulation capacity to Cr(III) and Cr(VI). Under 60 mg l(-1) Cr(III) and 10 mg l(-1) Cr(VI) treatment, there was no significant decrease of biomass in the leaves of L. hexandra (p>0.05). The highest bioaccumulation coefficients of the leaves for Cr(III) and Cr(VI) were 486.8 and 72.1, respectively. However, L. hexandra had a higher accumulation capacity for Cr(III) than for Cr(VI). At the Cr(III) concentration of 10 mg l(-1) in the culture solution, the concentration of chromium in leaves was 4868 mg kg(-1), while at the same Cr(VI) concentration, the concentration of chromium in leaves was only 597 mg kg(-1). These results confirmed that L. hexandra is a chromium hyperaccumulator which grows rapidly with a great tolerance to Cr and broad ecological amplitude. This species could provide a new plant resource that explores the mechanism of Cr hyperaccumulation, and has potential for usage in the phytoremediation of Cr-contaminated soil and water.     

Case studies on biological treatment of tannery effluents in India

This paper presents a comparative assessment of the cost and quality of treatment of tannery wastewater in India by two common effluent treatment plants (CETPs) constructed for two tannery clusters, at Jajmau (Kanpur) and at Unnao in the state of Uttar Pradesh, India. The Jajmau plant is upflow anaerobic sludge blanket (UASB) process-based, while the Unnao plant is activated sludge process (ASP)-based. Investigations indicated that the ASP-based plant was superior in all respects. Total annualized costs, including capital and operation and maintenance costs, for the UASB and ASP plants were Rs. 4.24 million/million liters per day (MLD) and Rs. 3.36 million/MLD, respectively. Land requirements for the two CETPs were 1.4 hectares/MLD and 0.95 hectares/ MLD, respectively. Moreover, the treated UASB effluent had higher biochemical and chemical oxygen demand (BOD/ COD) and considerable amounts of other undesirable constituents, like chromium (Cr) and sulfide, as compared with the ASP effluent, which had lower BOD/COD and negligible concentration of sulfide and Cr. Sludge production from the UASB-based plant was also higher at 1.4 t/day/MLD, in comparison to the sludge production of 0.8 t/day/MLD for the ASP-based plant. Also, the entire sludge produced in the UASB-based plant was Cr-contaminated and, hence, hazardous, while only a small fraction of the sludge produced in the ASP-based plant was similarly contaminated. The results of this study are at variance with the conventional wisdom of the superiority of anaerobic processes for tannery wastewater treatment in tropical developing countries like India.     

Photochemical reduction of hexavalent chromium in glycerol-containing solutions

Hexavalent chromium [Cr(VI)] in the form of potassium dichromate was photochemically reduced to trivalent chromium [Cr(III)] in aqueous solutions containing glycerol. This reaction occurred rapidly during irradiation with either unfiltered sunlight or a UVA-emitting light source. Photochemical reduction of Cr(VI) was pH-dependent and did not occur in dilute solutions of sodium hydroxide. In acidified solutions, the reduction occurred at elevated rates and at lower concentrations of glycerol. This reaction was found to be dependent on the unsubstituted alcohol groups of glycerol since alpha-phosphoglycerol and beta-phosphoglycerol did not support the photochemical reduction of Cr(VI). These findings suggest that glycerol or related polyols can be used for the remediation of hexavalent (toxic) chromium at contaminated environmental sites.     

Chromium transport, oxidation, and adsorption in manganese-coated sand

We examine how the processes of advection, dispersion, oxidation-reduction, and adsorption combine to affect the transport of chromium through columns packed with pyrolusite (beta-MnO2)-coated sand. We find that beta-MnO2 effectively oxidizes Cr(III) to Cr(VI) and that the extent of oxidation is sensitive to changes in pH, pore water velocity, and influent concentrations of Cr(III). Cr(III) oxidation rates, although initially high, decline well before the supply of beta-MnO2 is depleted, suggesting that a reaction product inhibits the conversion of Cr(III) to Cr(VI). Rate-limited reactions govern the weak adsorption of each chromium species, with Cr(III) adsorption varying directly with pH and Cr(VI) adsorption varying inversely with pH. The breakthrough data on chromium transport can be matched closely by calculations of a simple model that accounts for (1) advective-dispersive transport of Cr(III), Cr(VI), and dissolved oxygen, (2) first-order kinetics adsorption of the reduced and oxidized chromium species, and (3) nonlinear rate-limited oxidation of Cr(III) to Cr(VI). Our work supplements the limited database on the transport of redox-sensitive metals in porous media and provides a means for quantifying the coupled processes that contribute to this transport.