Oxidative transformations of environmental pharmaceuticals by Cl₂, ClO₂, O₃, and Fe(VI): kinetics assessment

Several pharmaceuticals have been detected globally in surface water and drinking water, which indicate their insufficient removal from water and wastewater using conventional treatment methods. This paper reviews the kinetics of oxidative transformations of pharmaceuticals (antibiotics, lipid regulators, antipyretics, anticonvulsants, and beta-blockers) by Cl(2), ClO(2), O(3), and ferrate(VI) (Fe(VI)O(4)(2-),Fe(VI)) under treatment conditions. In the chlorination of sulfonamide antibiotics, HOCl is the major reactive Cl(2) species whereas in the oxidation by Fe(VI), HFeO(4)(-) is the dominant reactive species. Both oxidation processes can oxidize sulfonamides in seconds at a neutral pH (t(1/2)≤ 220 s; 1 mg L(-1) HOCl or K(2)FeO(4)). The reactivity of O(3) with pharmaceuticals is generally higher than that of HOCl (k(app,pH 7) (O(3))=1-10(7)M(-1)s(-1); k(app,pH 7) (HOCl)=10(-2)-10(5)M(-1)s(-1)). Ozone selectively oxidizes pharmaceuticals and reacts mainly with activated aromatic systems and non-protonated amines. Oxidative transformation of most pharmaceuticals by O(3) occurs in seconds (t(1/2)≤ 100 s; 1 mg L(-1) O(3)) while half-lives for oxidations by HOCl differ by at least two orders of magnitude. Ozone appears to be efficient in oxidizing pharmaceuticals in aquatic environments. The limited work on Fe(VI) shows that it can also potentially transform pharmaceuticals in treatment processes.     

Kinetic assessment of the potassium ferrate(VI) oxidation of antibacterial drug sulfamethoxazole

Sulfamethoxazole (SMX), a worldwide-applied antibacterial drug, was recently found in surface waters and in secondary wastewater effluents, which may result in ecotoxical effects in the environment. Herein, removal of SMX by environmentally-friendly oxidant, potassium ferrate(VI) (K(2)FeO(4)), is sought by studying the kinetics of the reaction between Fe(VI) and SMX as a function of pH (6.93-9.50) and temperature (15-45 degrees C). The rate law for the oxidation of SMX by Fe(VI) is first-order with respect to each reactant. The observed second-order rate constant decreased non-linearly from 1.33+/-0.08 x 10(3) M(-1)s(-1) to 1.33+/-0.10 x 10(0) M(-1)s(-1) with an increase of pH from 7.00 to 9.50. This is related to protonation of Fe(VI) (HFeO(4)(-) <==> H(+) + FeO(4)(2-); pK(a,HFeO(4)) = 7.23) and sulfamethoxazole (SH <==> H(+) + S(-); pK(a,SH)=5.7). The estimated rate constants were k(11)(HFeO(4)(-) + SH) = 3.0 x 10(4) M(-1)s(-1), k(12)(HFeO(4)(-) + S(-)) = 1.7 x 10(2) M(-1)s(-1), and k(13) (FeO(4)(2-) + SH) = 1.2 x 10(0) M(-1)s(-1). The energy of activation at pH 7.0 was found to be 1.86+/-0.04 kJ mol(-1). If excess potassium ferrate(VI) concentration (10 microM) is used than the SMX in water, the half-life of the reaction using a rate constant obtained in our study would be approximately 2 min at pH 7. The reaction rates are pH dependent; thus, so are the half-lives of the reactions. The results suggest that K(2)FeO(4) has the potential to serve as an oxidative treatment chemical for removing SMX in water.     

Effect of ferrate on green algae removal

Green algae Cladophora aegagropila, present in cooling water of thermal power plants, causes many problems and complications, especially during summer. However, algae and its metabolites are rarely eliminated by common removal methods. In this work, the elimination efficiency of electrochemically prepared potassium ferrate(VI) on algae from cooling water was investigated. The influence of experimental parameters, such as Fe(VI) dosage, application time, pH of the system, temperature and hydrodynamics of the solution on removal efficiency, was optimized. This study demonstrates that algae C. aegagropila can be effectively removed from cooling water by ferrate. Application of ferrate(VI) at the optimized dosage and under the suitable conditions (temperature, pH) leads to 100% removal of green algae Cladophora from the system. Environmentally friendly reduction products (Fe(III)) and coagulation properties favour the application of ferrate for the treatment of water contaminated with studied microorganisms compared to other methods such as chlorination and use of permanganate, where harmful products are produced.

     

Reduction of ferrate(VI) and oxidation of cyanate in a Fe(VI)-TiO2-UV-NCO- system

The aqueous photocatalytic degradation of cyanate (NCO(-)), which is a long-lived neurotoxin formed during the remediation of cyanide in industrial waste streams, was studied in the ferrate(VI)-UV-TiO2-NCO(-) system. Kinetics measurements of the photocatalytic reduction of ferrate(VI) were carried out as a function of [NCO(-)], [ferrate(VI)], [O(2)], light intensity (I(o)), and amount of TiO2 in suspensions at pH 9.0. The photocatalytic reduction rate of ferrate(VI) in the studied system can be expressed as -d[Fe(VI)]/dt=kI(o)(0.5) [NCO(-)] [TiO2]. The rate of photocatalytic oxidation of cyanate with ferrate(VI) was greater than the rate in the analogous system without ferrate(VI). The possibility of involvement of reactive ferrate(V) species for this enhancement was determined by studying the reactivity of ferrate(V) with NCO(-) in a homogeneous solution using a premix pulse radiolysis technique. The rate constant for the reaction of ferrate(V) and NCO(-) in alkaline medium was estimated to be (9.60+/-0.07) x 10(2) M(-1) s(-1), which is much slower than the ferrate(VI) self-decomposition reaction (k approximately 10(7) M(-1) s(-1)). An analysis of the kinetic data in the Fe(VI)-UV-TiO2-NCO(-) system suggests that ferrate(V) is not directly participating in the oxidation of cyanate. Possible reactions in the system are presented to explain results of ferrate(VI) reduction and oxidation of cyanate.     

Ferrate(VI): green chemistry oxidant for degradation of cationic surfactant

Iron in its familiar form exists in the +2 and +3 oxidation states, however, higher oxidation state of iron +6, ferrate(VI) (Fe(VI)O(4)(2-)) can be obtained. The high oxidation power of ferrate(VI) can be utilized in developing cleaner ("greener") technology for remediation processes. This paper demonstrates the unique property of ferrate(VI) to degrade almost completely the cationic surfactant, cetylpyridinium chloride (C(5)H(5)N(+)(CH(2))(15)CH(3).H(2)O Cl(-), CPC). The Rate law for the oxidation of CPC by ferrate(VI) at pH 9.2 was found to be: -d[Fe(VI)]/dt = k[Fe(VI)][CPC](2). Ferrate(VI) oxidizes CPC within minutes and molar consumption of ferrate(VI) was nearly equal to the oxidized CPC. The decrease in total organic carbon (TOC) from CPC was more than 95%; suggesting mineralization of CPC to carbon dioxide. Ammonium ion was the other product of the oxidation. This is the first report in which Fe(VI)O(4)(2-) ion opens the pyridine ring and mineralizes the aliphatic chain of the organic molecule giving inorganic ions.     

Ferrate(VI) oxidation of zinc-cyanide complex

Zinc-cyanide complexes are found in gold mining effluents and in metal finishing rinse water. The effect of Zn(II) on the oxidation of cyanide by ferrate(VI) (Fe(VI)O(4)(2-), Fe(VI)) was thus investigated by studying the kinetics of the reaction of Fe(VI) with cyanide present in a potassium salt of a zinc cyanide complex (K(2)Zn(CN)(4)) and in a mixture of Zn(II) and cyanide solutions as a function of pH (9.0-11.0). The rate-law for the oxidation of Zn(CN)(4)(2-) by Fe(VI) was found to be -d[Fe(VI)]/dt=k[Fe(VI)][Zn(CN)(4)(2-)](0.5). The rate constant, k, decreased with an increase in pH. The effect of temperature (15-45 degrees C) on the oxidation was studied at pH 9.0, which gave an activation energy of 45.7+/-1.5kJmol(-1). The cyanide oxidation rate decreased in the presence of the Zn(II) ions. However, Zn(II) ions had no effect on the cyanide removal efficiency by Fe(VI) and the stoichiometry of Fe(VI) to cyanide was approximately 1:1; similar to the stoichiometry in absence of Zn(II) ions. The destruction of cyanide by Fe(VI) resulted in cyanate. The experiments on removal of cyanide from rinse water using Fe(VI) demonstrated complete conversion of cyanide to cyanate.     

Effectiveness of potassium ferrate (VI) as a green agent in the treatment and disinfection of carwash wastewater

Environmental Science and Pollution Research - Carwash wastewater treatment with potassium ferrate (VI) (K2FeO4) was optimized by response surface methodology. The optimum conditions for chemical...     

高铁酸钾预氧化并复合高岭土与PAC絮凝去除水中的颤藻

对高铁酸钾预氧化并复合高岭土与PAC絮凝法除水中颤藻的效果进行了研究。通过正交实验得出了在实验水质条件下,去除颤藻的最佳条件为:高铁酸钾的投加量2.4 mg/L、高岭土24 mg/L、PAC 5 mg/L及pH值为6.5。在此条件下,K2FeO4除藻效果明显优于传统的PAC絮凝工艺。考察了K2FeO4对接种到培养液中的颤藻生长活性的影响,结果表明,随着K2FeO4量的增加,颤藻生长活性抑制时间增长。数码生物显微镜观察表明:K2FeO4在低浓度2.4 mg/L下不能破坏颤藻细胞结构,高浓度50 mg/L下可使其细胞破裂死亡。     

Kinetics of the oxidation of sucralose and related carbohydrates by ferrate(VI)

The kinetics of the oxidation of sucralose, an emerging contaminant, and related monosaccharides and disaccharides by ferrate(VI) (Fe(VI)) were studied as a function of pH (6.5-10.1) at 25°C. Reducing sugars (glucose, fructose, and maltose) reacted faster with Fe(VI) than did the non-reducing sugar sucrose or its chlorinated derivative, sucralose. Second-order rate constants of the reactions of Fe(VI) with sucralose and disaccharides decreased with an increase in pH. The pH dependence was modeled by considering the reactivity of species of Fe(VI), (HFeO(4)(-) and FeO(4)(2-)) with the studied substrates. Second-order rate constants for the reaction of Fe(VI) with monosaccharides displayed an unusual variation with pH and were explained by considering the involvement of hydroxide in catalyzing the ring opening of the cyclic form of the carbohydrate at increased pH. The rate constants for the reactions of carbohydrates with Fe(VI) were compared with those for other oxidant species used in water treatment and were briefly discussed.     

Degradation of azo dyes using low iron concentration of Fenton and Fenton-like system

This study investigated Fenton and Fenton-like reactions at low iron concentration (相似文献   

Improved solubilization of activated sludge by ozonation in pressure cycles

The generation of a large volume of activated sludge (AS) from wastewater treatment has increasingly become a great burden on the environment. Anaerobic digestion is routinely practiced for excess waste sludge; however, the process retention time is long because of kinetic limitation in the hydrolysis step. We tested the feasibility of applying ozone in pressure cycles to enhance the disintegration and solubilization of AS with the goal to prepare them for digestion using reduced ozone dose and contact time. The AS was subjected to repetitive pressure cycles in a closed vessel in which an ozone gas mixture was compressed into the slurry to reach 1040 kPa in the headspace to be followed by rapid venting. For a returned AS with total COD (tCOD) of 8200 mg L(-1), a dose of 0.01 gO(3)g(-1) total suspended solids (TSS) delivered via 20 pressure cycles within 16 min resulted in a 37-fold increase of the sCOD/tCOD ratio (due to increased soluble COD, i.e. sCOD) and a 25% reduction of TSS, in comparison to a dose of 0.08 gO(3)g(-1) TSS via bubbling contact over 15 min that resulted in a 15-fold increase of the sCOD/tCOD ratio and a 12% reduction of TSS. Sludge solubilization was evidenced by increased dissolved contents of total phosphorous (from 10 to 64 mg L(-1)), total nitrogen (from 14 to 120 mg L(-1)), and protein (from <15 to 39 mg L(-1)) in the sludge suspension after treatment, indicating significant solubilization of AS.     

Occurrence and fate of heavy metals in the wastewater treatment process

The occurrence and the fate of heavy metals (Cd, Pb, Mn, Cu, Zn, Fe and Ni) during the wastewater treatment process were investigated in the wastewater treatment plant (WTP) of the city of Thessaloniki, northern Greece, operating in the activated sludge mode. For this purpose, wastewater and sludge samples were collected from six different points of the plant, namely, the influent (raw wastewater, RW), the effluent of the primary sedimentation tank (primary sedimentation effluent, PSE), the effluent of the secondary sedimentation tank (secondary sedimentation effluent, SSE), sludge from the primary sedimentation tank (primary sludge, PS), activated sludge from the recirculation stream (activated sludge, AS), and the digested/dewatered sludge (final sludge, FS).

The distribution of metals between the aqueous and the solid phase of wastewater was investigated. Good exponential correlation was found between the metal partition coefficient, logK_p, and the suspended solids concentration. The mass balance of heavy metals in the primary, secondary and the whole treatment process showed good closures for all metal species. The relative distribution of individual heavy metals in the treated effluent and the sludge streams indicated that Mn and Cu are primarily (>70%) accumulated in the sludge, while 47–63% of Cd, Cr, Pb, Fe, Ni and Zn remain in the treated effluent.     

Characterization of a simple bacterial consortium for effective treatment of wastewaters with reactive dyes and Cr(VI)

A microbial consortia consisting of three bacteria isolated from tanning and textile wastewaters revealed high capacity to simultaneously bioaccumulate dye and Cr(VI). The identity of the bacteria were determined by 16S rRNA gene analysis to be closely related to Ochrobactrium sp., Salmonella enterica and Pseudomonas aeruginosa. Dependence of initial pH values and range of concentrations of the dye Reactive Black B (33.2-103.1 mg l(-1)) and Cr(VI) (19.9-127.6 mg l(-1)) were examined to find the effect of pH on the dye and Cr(VI) bioaccumulation. Optimal pH for growth of the consortia in media containing 35 mg l(-1) dye and 50 mg l(-1) Cr(VI) was determined to be around 8. The Cr(VI) bioaccumulation by the consortia was rapid in media containing molasses with or without reactive dye with a maximum Cr(VI) bioaccumulation yield ranging from 90% to 99% within a 2-4d period. A slightly lower yield for the dye bioaccumulation was measured with a maximum dye bioaccumulation of 80% at 59.3 mg l(-1) dye and 69.8 mg l(-1) Cr(VI). The highest specific Cr uptake value was obtained as 76.7 mg g(-1) at 117.1 mg l(-1) Cr(VI) and 50.8 mg l(-1) dye concentration. This ability to bioaccumulate dye and Cr(VI) was more efficient than the enriched sludge from which they were isolated.     

Sources of adsorbable organic halogens (AOX) in sludge of Gaza

Average concentrations of adsorbable organic halogens (AOX) in sludge from the Gaza Strip reached 600 mg kg(-1) which currently represents a major limiting factor for sludge application in agriculture. This study aims to identify the main sources of AOX in Gaza where the area is small with limited industrial activities. The results showed that the AOX in effluent sludge is formed mainly inside the treatment plant. Although the plant receives AOX wastewater of only 85 microg l(-1), this value increased five fold inside the plant to an average of 400 microg l(-1) in the effluent wastewater. On the other hand, the sludge from the first sedimentation pond showed an AOX concentration of 213 mg kg(-1) and increased in the final sedimentation pond to 500 mg kg(-1). The AOX concentration in three month old sludge was 130 mg kg(-1). The textile and detergent industries are the major AOX producing industries in Gaza, with an average AOX of 40,000 microg l(-1) in their effluent wastewater. These values do not represent a significant AOX pollution load to the treatment plant because these industries are very limited and their effluents are diluted before entering the municipal treatment plant. Industrial activity decreased in 2006 to less than 70% of the previous four years. Consequently, the AOX in the industrial effluent decreased from 150,000 to 40,000 microg l(-1) over the same time period. Sludge from these industries showed 1300 mg kg(-1) AOX for the past four years and only 400 mg kg(-1) in 2006. Moreover, the AOX in the influent wastewater discharged to the treatment plant decreased from 320 to 85 microg l(-1) for the same period. This study revealed that the major AOX is formed inside the treatment plant and especially in the anaerobic facilities. There was no correlation between the AOX concentrations in the sludge and the wastewater at the same location. Moreover, there was no correlation between the AOX in sludge/wastewater and dissolved oxygen, pH and chloride in that treatment plant.     

Electrokinetic enhancement removal of heavy metals from industrial wastewater sludge

An enhanced electrokinetic process for removal of metals (Cr, Cu, Fe, Ni, Pb, Zn) from an industrial wastewater sludge was performed. The electrokinetic experiments were conducted under a constant potential gradient (1.25 V cm(-1)) with processing fluids of tap water (TW), sodium dodecylsulfate (SDS) and citric acid (CA) for 5 days. Results showed that metal removal efficiency of heavy metals for EK-TW, EK-SDS and EK-CA systems are 11.2-60.0%, 37.2-76.5%, and 43.4-78.0%, respectively. A highest metal removal performance was found in EK-CA system. The removal priority of investigated metals from sludge by EK process was found as: Cu > Pb > Ni > Fe > Zn > Cr. The results of sequential extraction analysis revealed that the binding forms of heavy metals with sludge after electrokinetic process were highly depend upon the processing fluid operated. It was found that the binding forms of metals with sludge were changed from the more difficult extraction type (residual and sulfate fractions) to easier extraction types (exchangeable, sorbed, and organic fraction) after treatment by electrokinetic process. Results imply that if a proper treatment technology is followed by this EK process to remove metals more effectively, this treated sludge will be more beneficial for sludge utilization afterwards. Before it was reused, the risk associated with metals of more mobile forms to the environment need to be further investigated. The cost analysis was also evaluated for the investigated electrokinetic systems.     

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.     

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%.     

Ferrate(VI) enhanced photocatalytic oxidation of pollutants in aqueous TiO<Subscript>2</Subscript> suspensions

Background, aim and scope  

Photocatalytic oxidation using UV irradiation of TiO₂ has been studied extensively and has many potential industrial applications, including the degradation of recalcitrant contaminants in water and wastewater treatment. A limiting factor in the oxidation process is the recombination of conduction band electrons (e ⁻ _cb) with electron holes (h_vb⁺) on the irradiated TiO₂ surface; thus, in aqueous conditions, the presence of an effective electron scavenger will be beneficial to the efficiency of the oxidation process. Ferrate (FeO₄²⁻) has received much recent attention as a water treatment chemical since it behaves simultaneously as an oxidant and coagulant. The combination of ferrate [Fe(VI)] with UV/TiO₂ photocatalysis offers an oxidation synergism arising from the Fe(VI) scavenging of e ⁻ _cb and the corresponding beneficial formation of Fe(V) from the Fe(VI) reduction. This paper reviews recent studies concerning the photocatalytic oxidation of problematic pollutants with and without ferrate.     

高铁酸盐氧化降解水中苯酚的动力学及机理研究

以自制高铁酸钾(K₂FeO₄)为原料，探讨了影响高铁酸盐氧化降解苯酚的主要因素，并研究了苯酚降解的动力学特征和反应机理。结果表明，高铁酸盐加入量、pH值、持续搅拌、反应温度、反应时间都影响苯酚去除效果。其中高铁酸盐加入量是影响苯酚去除效果的关键因素，高铁酸盐氧化降解苯酚的最佳pH值范围为9～10，持续搅拌和提高反应温度只影响苯酚降解速率而不影响苯酚降解率。苯酚的降解过程遵循一级反应动力学模型。苯酚被高铁酸盐氧化生成CO₂、H₂O以及一部分难矿化的有机物。