Biosorption of Cr(III) from aqueous solution by freeze-dried activated sludge: Equilibrium,kinetic and thermodynamic studies

Batch biosorption experiments were conducted to remove Cr(III) from aqueous solutions using activated sludge from a sewage treatment plant. An investigation was conducted on the effects of the initial pH, contact time, temperature, and initial Cr(III) concentration in the biosorption process. The results revealed that the activated sludge exhibited the highest Cr(III) uptake capacity (120 mg·g⁻¹) at 45°C, initial pH of 4, and initial Cr(III) concentration of 100 mg·L⁻¹. The biosorption results obtained at various temperatures showed that the biosorption pattern accurately followed the Langmuir model. The calculated thermodynamic parameters, ΔG^o (−0.8– −4.58 kJ·mol⁻¹), ΔH^o (15.6–44.4 kJ·mol⁻¹), and ΔS^o (0.06–0.15 kJ·mol⁻¹·K⁻¹) clearly indicated that the biosorption process was feasible, spontaneous, endothermic, and physical. The pseudo first-order and second-order kinetic models were adopted to describe the experimental data, which revealed that the Cr(III) biosorption process conformed to the second-order rate expression and the biosorption rate constants decreased with increasing Cr(III) concentration. The analysis of the values of biosorption activation energy (E_a = −7 kJ·mol⁻¹) and the intra-particle diffusion model demonstrated that Cr(III) biosorption was film-diffusion-controlled.     

Ultrasound-assisted emulsification solidified floating organic drop microextraction for the determination of trace amounts of copper in water samples

A simple and efficient liquid-phase microextraction (LPME) technique was developed using ultrasound-assisted emulsification solidified floating organic drop microextraction (USAE-SFODME) combined with flame atomic absorption spectrometry, for the extraction and determination of trace copper in water samples. 1-(2-Pyridylazo)-2-naphthol (PAN) was used as chelating agent. Microextraction efficiency factors (including extraction solvent type, extraction volume, time, temperature, and pH), the amount of the chelating agent, and salt effect were investigated and optimized. Under the optimum extraction conditions, figures of merit of the proposed method were evaluated. The calibration graph was linear in the range of 20–600 mg·L⁻¹ with a detection limit of 0.76 mg·L⁻¹. The relative standard deviation (R.S.D) for ten replicate measurements of 20 and 400 mg·L⁻¹ of copper was 3.83% and 2.65%, respectively. Finally, the proposed method was applied to tap water, river water, and sea water, and accuracy was assessed through the analysis of certified reference water or recovery experiments.     

Perfluorocarboxylic acids (PFCAs) and perfluoroalkyl sulfonates (PFASs) in surface and tap water around Lake Taihu in China

Perfluorinated compounds (PFCs) are ubiquitously distributed in the environment mainly as perfluoro-carboxylic acids (PFCAs) and perfluoroalkyl sulfonates (PFASs). In this paper, six PFCAs and two PFASs were quantified in surface and tap water samples from 12 sites around Lake Taihu near Shanghai City in East China. Predominant PFCs were perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), of which the concentration ranges were 6.8–206 and 1.2–45 ng·L⁻¹, the geometric means were 35.3 and 9.4 ng·L⁻¹, and the median (quartile range) values were 31.4 (34.4) and 10.4 (10.7) ng·L⁻¹, respectively. Other PFCs were also detected but in much lower concentrations than PFOA. The sources of the PFCs were expected to be direct industrial discharges in the Lake Taihu area, and this area was also a possible source of PFCs contaminations in Shanghai district in the downstream. PFCs distributions were found different in the upstream, downstream and north part of Lake Taihu. Occurrences of PFCs in the tap water in Lake Taihu area indicated their exposure to the local people. A brief estimation of the environmental risks by PFCs implied no acute or immediate risks from PFCs to local human health, but chronic risks from PFOA in the tap water should be considered in the downstream regions.     

Phenanthrene sorption to environmental black carbon in sediments from the Song-Liao watershed (China)

Black carbon (BC) in ten contaminated sediments from the Song-Liao watershed, NE China, was isolated upon treatments using a combustion method at 375°C, and the isolates’ sorption isotherms for phenanthrene (Phen) were determined. All sorption isotherms were nonlinear and fitted well by the Freundlich model. A negative relation was found between Freundlich sorption nonlinearity parameter (n values) and BC/total organic carbon (TOC) content of the original sediments (r²=0.687, p<0.01), indicating the dominance of BC in Phen sorption nonlinearity. The BC isolates from this industrialized region had n values of 0.342 to 0.505 and logK_FOC values of 6.02 to 6.42(μg·kg⁻¹·OC⁻¹)/(μg·L⁻¹) ⁿ for Phen. At a given C_e, the BC had higher K_oc value than the original sediments, revealing a higher sorption capacity for BC. BC was responsible for 50.0% to 87.3% of the total sorption at C_e=0.05 S_w, clearly indicating the dominance of BC particles in overall sorption of Phen by sediments.     

Oxidation and biotoxicity assessment of microcystin-LR using different AOPs based on UV,O3 and H2O2

MC-LR removal performances under different AOPs were compared systematically. Higher removal efficiency and synergistic effects were obtained by combined process. The acute biotoxicity raised in different degrees after oxidation. Microcystin-LR attracts attention due to its high toxicity, high concentration and high frequency. The removal characteristics of UV/H₂O₂ and O₃/H₂O₂ advanced oxidation processes and their individual process for MC-LR were investigated and compared in this study. Both the removal efficiencies and rates of MC-LR as well as the biotoxicity of degradation products was analyzed. Results showed that the UV/H₂O₂ process and O₃/H₂O₂ were effective methods to remove MC-LR from water, and they two performed better than UV-, O₃-, H₂O₂-alone processes under the same conditions. The effects of UV intensity, H₂O₂ concentration and O₃ concentration on the removal performance were explored. The synergistic effects between UV and H₂O₂, O₃ and H₂O₂ were observed. UV dosage of 1800 mJ·cm⁻² was required to remove 90% of 100 mg·L⁻¹ MC-LR, which amount significantly decreased to 500 mJ·cm⁻² when 1.7 mg·L⁻¹ H₂O₂ was added. 0.25 mg·L⁻¹ O₃, or 0.125 mg·L⁻¹ O₃ with 1.7 mg·L⁻¹ H₂O₂ was needed to reach 90% removal efficiency. Furthermore, the biotoxicity results about these UV/H₂O₂, O₃/H₂O₂ and O₃-alone processes all present rising trends with oxidation degree of MC-LR. Biotoxicity of solution, equivalent to 0.01 mg·L⁻¹ Zn²⁺, raised to 0.05 mg·L⁻¹ Zn²⁺ after UV/H₂O₂ or O₃/H₂O₂ reaction. This phenomenon may be attributed to the aldehydes and ketones with small molecular weight generated during reaction. Advice about the selection of MC-LR removal methods in real cases was provided.     

Impact of solids on biphasic biodegradation of phenanthrene in the presence of hydroxypropyl- &#946; -cyclodextrin (HPCD)

The consequence of polycyclic aromatic hydrocarbons (PAHs) in the environment is of great concern. The hydrophobic properties of PAHs significantly impact phase distribution causing limited bioavailability. Enhanced biodegradation has been extensively carried out by surfactants and the redeployment effect was recognized. However, the quantitative relationship concerning the impact of solids was rarely reported. A batch of biphasic tests were carried out by introducing Mycobacterium vanbaalenii PYR-1 and hydroxypropyl-β-cyclodextrin (HPCD) into a mixture of phenanthrene solution and various glass beads (GB37-63, GB105-125, and GB350-500). The comparative results demonstrated that HPCD had little effect on microbial growth and was not degradable by bacterium. A model was proposed to describe the biodegradation process. The regression results indicated that the partition coefficient k_d (1.234, 0.726 and 0.448 L·g⁻¹) and the degradation rate k (0 mmol·L⁻¹: 0.055, 0.094, and 0.112; 20 mmol·L⁻¹: 0.126, 0.141, and 0.156; 40 mmol·L⁻¹: 0.141, 0.156 and 0.184 d⁻¹) were positively and negatively correlated with the calculated total surface area (TSA) of solids, respectively. Degradation enhanced in the presence of HPCD, and the enhancing factor f was calculated (20 mmol·L⁻¹: 15.16, 40.01, and 145.5; 40 mmol·L⁻¹: 13.29, 37.97, and 138.4), indicating that the impact of solids was significant for the enhancement of biodegradation.     

Recent advances in membrane bioreactor technology for wastewater treatment in China

Since the introduction of the membrane bioreactor (MBR) in China in the early 1990s, remarkable progress has been achieved on the research and application of this technology. China has now become one of the most active fields in the world in this regard. This review outlines the development of MBR-based processes in China and their performance of treating municipal and industrial wastewaters. Since membrane fouling is a critical operational problem with MBR processes, this paper also proposes updated understanding of fouling mechanisms and strategies of fouling control, which are mainly compiled from publications of Chinese researchers. As for the commercial application of MBR in the country, the latest statistics of large-scale MBR plants (>10000 m³·d⁻¹) are provided, and the growth trend of total treatment capacity as well as its driving force is analyzed.     

The combined effects of biomass and temperature on maximum specific ammonia oxidation rate in domestic wastewater treatment

• Actual SAORs was determined using MLVSS and temperature. • Measured SAOR decreased with increasing MLVSS 1.1‒8.7 g/L. • Temperature coefficient (θ) decreased with increasing MLVSS. • Nitrification process was dynamically simulated based on laboratory-scale SBR tests. • A modified model was successfully validated in pilot-scale SBR systems. Measurement and predicted variations of ammonia oxidation rate (AOR) are critical for the optimization of biological nitrogen removal, however, it is difficult to predict accurate AOR based on current models. In this study, a modified model was developed to predict AOR based on laboratory-scale tests and verified through pilot-scale tests. In biological nitrogen removal reactors, the specific ammonia oxidation rate (SAOR) was affected by both mixed liquor volatile suspended solids (MLVSS) concentration and temperature. When MLVSS increased 1.6, 4.2, and 7.1-fold (1.3‒8.9 g/L, at 20°C), the measured SAOR decreased by 21%, 49%, and 56%, respectively. Thereby, the estimated SAOR was suggested to modify when MLVSS changed through a power equation fitting. In addition, temperature coefficient (θ) was modified based on MLVSS concentration. These results suggested that the prediction of variations ammonia oxidation rate in real wastewater treatment system could be more accurate when considering the effect of MLVSS variations on SAOR.     

Comparison of membrane fouling in ultrafiltration of down-flow and up-flow biological activated carbon effluents

The UF membrane fouling by down- and up-flow BAC effluents were compared. Up-flow BAC effluent fouled the membrane faster than down-flow BAC effluent. The combined effects dominated irreversible fouling. The extent of fouling exacerbated by inorganic particles was higher. The TMP, permeate flux, and normalized membrane flux during 21 days of UF of DBAC and UBAC effluents. Fouling during ultrafiltration of down- and up-flow biological activated carbon effluents was investigated to determine the roles of polysaccharides, proteins, and inorganic particles in ultrafiltration membrane fouling. During ultrafiltration of down- flow biological activated carbon effluent, the trans-membrane pressure was≤26 kPa and the permeate flux was steady at 46.7 L?m⁻²?h⁻¹. However, during ultrafiltration of up-flow biological activated carbon effluent, the highest trans-membrane pressure was almost 40 kPa and the permeate flux continuously decreased to 30 L?m⁻²?h⁻¹. At the end of the filtration period, the normalized membrane fluxes were 0.88 and 0.62 for down- and up-flow biological activated carbon effluents, respectively. The membrane removed the turbidity and polysaccharides content by 47.4% and 30.2% in down- flow biological activated effluent and 82.5% and 22.4% in up-flow biological activated carbon effluent, respectively, but retained few proteins. The retention of polysaccharides was higher on the membrane that filtered the down- flow biological activated effluent compared with that on the membrane that filtered the up-flow biological activated carbon effluent. The polysaccharides on the membranes fouled by up-flow biological activated carbon and down- flow biological activated effluents were spread continuously and clustered, respectively. These demonstrated that the up-flow biological activated carbon effluent fouled the membrane faster. Membrane fouling was associated with a portion of the polysaccharides (not the proteins) and inorganic particles in the feed water. When there was little difference in the polysaccharide concentrations between the feed waters, the fouling extent was exacerbated more by inorganic particles than by polysaccharides.     

低碳氮比废水好氧颗粒污泥系统稳定性及微生物种群多样性研究

低碳氮比(C/N)废水处理是含氮废水处理中的难题之一.本实验在C/N为4:1和2:1(COD和NH₄⁺-N浓度分别为400 mg·L^-1和100 mg·L^-1,400 mg·L^-1和200 mg·L^-1)条件下,考察好氧颗粒污泥系统对低碳氮比废水的处理效果、长期运行稳定性,研究C/N对好氧颗粒微生物结构变化的影响.研究结果表明,在C/N为4:1的废水中接种活性污泥培养好氧颗粒污泥,形成的颗粒沉降性能良好,MLSS为4.94 g·L^-1,SVI30为40 mL·g^-1,COD去除率90%以上,氨氮去除率接近100%.降低碳氮比,即C/N为2:1后,好氧颗粒的物理及硝化性能无明显变化,MLSS为11.38 g·L^-1,SVI₃₀/SVI₅维持在1左右,COD去除率大于85%,氨氮去除率98%.碳氮比降低使颗粒微生物多样性减少,其中陶厄氏菌受影响较小,而硝化功能菌出现更替:噬氢菌、食酸菌、里德拜特氏菌消失,鞘氨醇单胞菌、束缚杆菌等成为优势菌种.实验表明,该低碳氮比条件下好氧颗粒污泥系统能够稳定运行,且具有优良的处理性能.     

Ozonation of the 5-fluorouracil anticancer drug and its prodrug capecitabine: Reaction kinetics,oxidation mechanisms,and residual toxicity

Specific second-order rate constants were determined for 5-FU and CAP with ozone. Reaction sites were confirmed by kinetics, Fukui analysis, and products. The olefin moiety was the main ozone reaction site for 5-FU and CAP. Carboxylic acids comprised most of the residual TOC for 5-FU. Ozonation removed the toxicity associated with 5-FU and products but not CAP. Anticancer drugs (ADs) have been detected in the environment and represent a risk to aquatic organisms, necessitating AD removal in drinking water and wastewater treatment. In this study, ozonation of the most commonly used antimetabolite ADs, namely 5-fluorouracil (5-FU) and its prodrug capecitabine (CAP), was investigated to determine reaction kinetics, oxidation mechanisms, and residual toxicity. The specific second-order rate constants between aqueous ozone and 5-FU, 5-FU⁻, 5-FU²⁻, CAP, and CAP⁻ were determined to be 7.07(±0.11)×10⁴ M⁻¹·s⁻¹, 1.36(±0.06)×10⁶ M⁻¹·s⁻¹, 2.62(±0.17)×10⁷ M⁻¹·s⁻¹, 9.69(±0.08)×10³ M⁻¹·s⁻¹, and 4.28(±0.07)×10⁵ M⁻¹·s⁻¹, respectively; furthermore, the second-order rate constants for ^•OH reaction with 5-FU and CAP at pH 7 were determined to be 1.85(±0.20)×10⁹ M⁻¹·s⁻¹ and 9.95(±0.26)×10⁹ M⁻¹·s⁻¹, respectively. Density functional theory was used to predict the main ozone reaction sites of 5-FU (olefin) and CAP (olefin and deprotonated secondary amine), and these mechanisms were supported by the identified transformation products. Carboxylic acids constituted a majority of the residual organic matter for 5-FU ozonation; however, carboxylic acids and aldehydes were important components of the residual organic matter generated by CAP. Ozone removed the toxicity of 5-FU to Vibrio fischeri, but the residual toxicity of ozonated CAP solutions exhibited an initial increase before subsequent removal. Ultimately, these results suggest that ozone is a suitable technology for treatment of 5-FU and CAP, although the residual toxicity of transformation products must be carefully considered.     

Sorption and desorption of pymetrozine on six Chinese soils

Pymetrozine is a selective insecticide with a unique chemical structure and mode to control hemipteran and homopteran. While pymetrozine has brought great benefits to crop production by killing insects, its residues in soil may have a detrimental effect on environment. Therefore, it is of great importance to investigate its behaviors in soil. In this study, the sorption and desorption of pymetrozine on six Chinese soils were investigated using a batch equilibrium approach to understand its mobile behavior in the soils. Both sorption and desorption isotherms of pymetrozine were in good agreement with the Freundlich model. The sorption coefficient K_F varied between 3.37 and 58.32 mL∙g⁻¹ and the sorption isotherms were nonlinear, with 1/n ranging from 0.57 to 0.91. A regression equation was proposed to predict the sorption of pymetrozine on six different soil samples: log K_F = 4.3708 − 4.5709 × log (pH in 0.01mol·L⁻¹ CaCl₂) + 0.4700 × log OC% + 0.0057 × sand (%) + 0.0022 × CEC(clay), with R² = 0.9982. The organic carbon content of soil positively affected the sorption of pymetrozine, but soil pH had a negative effect on the sorption. Additionally, effects of CaCl₂ concentration, soil to solution ratio and pesticide form were investigated. The sorption was promoted with an increase in soil to solution ratio and a decrease in CaCl₂ concentration. The possible variation of the five formulated products of pymetrozine was also investigated.     

Modified landfill gas generation rate model of first-order kinetics and two-stage reaction

This investigation was carried out to establish a new domestic landfill gas (LFG) generation rate model that takes into account the impact of leachate recirculation. The first-order kinetics and two-stage reaction (FKTSR) model of the LFG generation rate includes mechanisms of the nutrient balance for biochemical reaction in two main stages. In this study, the FKTSR model was modified by the introduction of the outflow function and the organic acid conversion coefficient in order to represent the in-situ condition of nutrient loss through leachate. Laboratory experiments were carried out to simulate the impact of leachate recirculation and verify the modified FKTSR model. The model calibration was then calculated by using the experimental data. The results suggested that the new model was in line with the experimental data. The main parameters of the modified FKTSR model, including the LFG production potential (L₀), the reaction rate constant in the first stage (K₁), and the reaction rate constant in the second stage (K₂) of 64.746 L, 0.202 d⁻¹, and 0.338 d⁻¹, respectively, were comparable to the old ones of 42.069 L, 0.231 d⁻¹, and 0.231 d⁻¹. The new model is better able to explain the mechanisms involved in LFG generation.     

Engineering application of membrane bioreactor for wastewater treatment in China: Current state and future prospect

China has been the forerunner of large-scale membrane bioreactor （MBR） application. Since the first large-scale MBR （≥ 10 000 m^3·d^-1） was put into operation in 2006, the engineering implementation of MBR in China has attained tremendous development. This paper outlines the commercial application of MBR since 2006 and provides a variety of engineering statistical data, covering the fields of municipal wastewater, industrial wastewater, and polluted surface water treatment. The total treatment capacity of MBRs reached 1× 10^6 m^3·d^-1 in 2010, and has currently exceeded 4.5 × 10^6 m^3·d^-1 with -75% of which pertaining to municipal wastewater treatment. The anaerobic/anoxic/aerobie-MBR and its derivative processes have been the most popular in the large-scale municipal application, with the process features and typical ranges of parameters also presented in this paper. For the treatment of various types of industrial wastewater, the configurations of the MBR-based processes are delineated with representative engineering cases. In view of the significance of the cost issue, statistics of capital and operating costs are also provided, including cost structure and energy composition. With continuous stimulation from the environmental stress, political propulsion, and market demand in China, the total treatment capacity is expected to reach 7.5 × 10^6 m^3·d^-1 by 2015 and a further expansion of the market is foreseeable in the next five years. However, MBR application is facing several challenges, such as the relatively high energy consumption. Judging MBR features and seeking suitable application areas should be of importance for the long-term development of this technology.     

Comparison of different valent iron on anaerobic sludge digestion: Focusing on oxidation reduction potential,dissolved organic nitrogen and microbial community

• ORP value from −278.71 to −379.80 mV showed indiscernible effects on methane yield. • Fe(II) and Fe(III) promoted more degradation of proteins and amino acids than Fe⁰. • The highest enrichment of Geobacter was noted in samples added with Fe⁰. • Cysteine was accumulated during iron enhanced anaerobic sludge digestion. • Both iron content and valence were important for methane production. This study compared effects of three different valent iron (Fe⁰, Fe(II) and Fe(III)) on enhanced anaerobic sludge digestion, focusing on the changes of oxidation reduction potential (ORP), dissolved organic nitrogen (DON), and microbial community. Under the same iron dose in range of 0−160 mg/L after an incubation period of 30 days (d), the maximum methane production rate of sludge samples dosed with respective Fe⁰, Fe(II) and Fe(III) at the same concentration showed indiscernible differences at each iron dose, regardless of the different iron valence. Moreover, their behavior in changes of ORP, DON and microbial community was different: (1) the addition of Fe⁰ made the ORP of sludge more negative, and the addition of Fe(II) and Fe(III) made the ORP of sludge less negative. However, whether being more or less negative, the changes of ORP may show unobservable effects on methane yield when it ranged from −278.71 to −379.80 mV; (2) the degradation of dissolved organic nitrogen, particularly proteins, was less efficient in sludge samples dosed with Fe⁰ compared with those dosed with Fe(II) and Fe(III) after an incubation period of 30 d. At the same dose of 160 mg/L iron, more cysteine was noted in sludge samples dosed with Fe(II) (30.74 mg/L) and Fe(III) (27.92 mg/L) compared with that dosed with Fe⁰ (21.75 mg/L); (3) Fe⁰ particularly promoted the enrichment of Geobacter, and it was 6 times higher than those in sludge samples dosed with Fe(II) and Fe(III) at the same dose of 160 mg/L iron.     

Optimization of thermophilic anaerobic-aerobic treatment system for Palm Oil Mill Effluent (POME)

Optimization of an integrated anaerobic-aerobic bioreactor (IAAB) treatment system for the reduction of organic matter (Chemical Oxygen Demand (COD), Biochemical Oxygen Demand (BOD) and Total Suspended Solids (TSS) concentrations) in Palm Oil Mill Effluent (POME) to legal standards with high methane yield was performed for the first time under thermophilic condition (50°C–55°C) by using response surface methodology (RSM). The experiments were conducted based on a central composite rotatable design (CCRD) with three independent operating variables, organic loading rates in anaerobic compartment (OLR_an) and mixed liquor volatile suspended solids (MLVSS) concentration in anaerobic (MLVSS_an) and aerobic compartments (MLVSS_a). The optimum conditions for the POME treatment were determined as OLR_an of 15.6 g COD·L^-1·d^-1, MLVSS_an of 43100 mg·L^-1, and MLVSS_a of 18600 mg·L^-1, where high aerobic COD, BOD and TSS removal efficiencies of 96.3%, 97.9%, and 98.5% were achieved with treated BOD of 56 mg·L^-1 and TSS of 28 mg·L^-1 meeting the discharge standard. This optimization study successfully achieved a reduction of 42% in the BOD concentrations of the final treated effluent at a 48% higher OLR_an as compared to the previous works. Besides, thermophilic IAAB system scores better feasibility and higher effectiveness as compared to the optimized mesophilic system. This is due to its higher ability to handle high OLR with higher overall treatment efficiencies (more than 99.6%), methane yield (0.31 L CH₄·g^-1 COD_removed) and purity of methane (67.5%). Hence, these advantages ascertain the applicability of thermophilic IAAB in the POME treatment or even in other high-strength wastewaters treatment.     

臭氧污泥减量过程中混合液各参数的变化

实验用污泥的初始浓度(MLSS)分别限定为4g/L、7g/L和11g/L,用以探讨不同浓度下臭氧氧化过程中COD、N和P浓度的变化。结果表明:臭氧氧化过程中,MLSS和MLVSS基本呈线性下降;臭氧对污泥细胞的溶解可以引起混合液中COD、N和P浓度的升高,升高速率受污泥浓度和臭氧浓度影响较大;TKN和硝态氮是N的主要存在形式,TKN和TN随时间均呈先增加后趋缓的变化规律;臭氧对氨氮和亚硝酸盐氮有较强的氧化能力,二者浓度均呈先增大后减小的规律;而硝酸盐氮呈一直增加趋势;臭氧对COD的氧化也很明显,表现为COD的增加速率随氧化时间的增加而不断降低;总磷的浓度基本呈线性增加,单位质量污泥的总磷释放量差异不大;臭氧对MLSS的彻底减量会引起臭氧溶胞利用率的降低,因此应该合理控制臭氧化反应的时间。     

Ozonation as an efficient pretreatment method to alleviate reverse osmosis membrane fouling caused by complexes of humic acid and calcium ion

Humic acids (HA) didn’t cause obvious reverse osmosis (RO) membrane fouling in 45 h. Osmotic pressure (NaCl) affected slightly the RO membrane fouling behavior of HA. Ca²⁺ promoted aggregation of HA molecules and thus aggravated RO membrane fouling. Ozonation eliminated the effect of Ca²⁺ on the RO membrane fouling behavior of HA. The change of the structure of HA was related to its membrane fouling behavior. Humic acid has been considered as one of the most significant sources in feed water causing organic fouling of reverse osmosis (RO) membranes, but the relationship between the fouling behavior of humic acid and the change of its molecular structure has not been well developed yet. In this study, the RO membrane fouling behavior of humic acid was studied systematically with ozonation as a pretreatment method to control RO membrane fouling. Furthermore, the effect of ozone on the structure of humic acid was also explored to reveal the mechanisms. Humic acid alone (10–90 mg/L, in deionized water) was found not to cause obvious RO membrane fouling in 45-h operation. However, the presence of Ca²⁺ aggravated significantly the RO membrane fouling caused by humic acid, with significant flux reduction and denser fouling layer on RO membrane, as it was observed by scanning electron microscope (SEM) and atomic force microscope (AFM). However, after the pretreatment by ozone, the influence of Ca²⁺ was almost eliminated. Further analysis revealed that the addition of Ca²⁺ increased the particle size of humic acid solution significantly, while ozonation reduced the SUVA₂₅₄, particle size and molecular weight of the complexes of humic acid and Ca²⁺ (HA-Ca²⁺ complexes). According to these results and literature, the bridge effect of Ca²⁺ aggregating humic acid molecules and the cleavage effect of ozone breaking HA-Ca²⁺ complexes were summarized. The change of the structure of humic acid under the effect of Ca²⁺ and ozone is closely related to the change of its membrane fouling behavior.     

Process control factors for continuous microbial perchlorate reduction in the presence of zero-valent iron

Process control parameters influencing microbial perchlorate reduction via a flow-through zero-valent iron （ZVI） column reactor were investigated in order to optimize perchlorate removal from water. Mixed perchlorate reducers were obtained from a wastewater treatment plant and inoculated into the reactor without further acclimation. Examined parameters included hydraulic residence time （HRT）, pH, nutrients requirement, and perchlorate reduction kinetics. The minimum HRT for the system was concluded to be 8 hr. The removal efficiency of 10 mg. L-1 influent perchlorate concentration was reduced by 20%-80% without control to the neutral pH （HRT = 8 hr）. Therefore pH was determined to be an important parameter for microbial perchlorate reduction. Furthermore, a viable alternative to pH buffer was discussed. The microbial perchlorate reduction followed the first order kinetics, with a rate constant （K） of 0.761 hr-1. The results from this study will contribute to the implementation of a safe, cost effective, and efficient system for perchlorate reduction to below regulated levels.     

Using loose nanofiltration membrane for lake water treatment: A pilot study

• A pilot study was conducted for drinking water treatment using loose NF membranes. • The membranes had very high rejection of NOM and medium rejection of Ca²⁺/Mg²⁺. • Organic fouling was dominant and contribution of inorganic fouling was substantial. • Both organic and inorganic fouling had spatial non-uniformity on membrane surface. • Applying EDTA at basic conditions was effective in removing membrane fouling. Nanofiltration (NF) using loose membranes has a high application potential for advanced treatment of drinking water by selectively removing contaminants from the water, while membrane fouling remains one of the biggest problems of the process. This paper reported a seven-month pilot study of using a loose NF membrane to treat a sand filtration effluent which had a relatively high turbidity (~0.4 NTU) and high concentrations of organic matter (up to 5 mg/L as TOC), hardness and sulfate. Results showed that the membrane demonstrated a high rejection of TOC (by>90%) and a moderately high rejection of two pesticides (54%–82%) while a moderate rejection of both calcium and magnesium (~45%) and a low rejection of total dissolved solids (~27%). The membrane elements suffered from severe membrane fouling, with the membrane permeance decreased by 70% after 85 days operation. The membrane fouling was dominated by organic fouling, while biological fouling was moderate. Inorganic fouling was mainly caused by deposition of aluminum-bearing substances. Though inorganic foulants were minor contents on membrane, their contribution to overall membrane fouling was substantial. Membrane fouling was not uniform on membrane. While contents of organic and inorganic foulants were the highest at the inlet and outlet region, respectively, the severity of membrane fouling increased from the inlet to the outlet region of membrane element with a difference higher than 30%. While alkaline cleaning was not effective in removing the membrane foulants, the use of ethylenediamine tetraacetate (EDTA) at alkaline conditions could effectively restore the membrane permeance.