Factors influencing antibiotics adsorption onto engineered adsorbents

The study evaluated the adsorption of two antibiotics by four engineered adsorbents (hypercrosslinked resin MN-202, macroporous resin XAD-4, activated carbon F-400, and multi-walled carbon nanotubes (MWCNT)) from aqueous solutions. The dynamic results demonstrated the dominant influence of pore size in adsorption. The adsorption amounts of antibiotics on XAD-4 were attributed to the hydrophobic effect, whereas steric hindrance or micropore-filling played a main role in the adsorption of antibiotics by F-400 because of its high microporosity. Aside from F-400, similar patterns of pH-dependent adsorption were observed, implying the importance of antibiotic molecular forms to the adsorption process for adsorbents. Increasing the ionic concentration with CaCl2 produced particular adsorption characteristics on MWCNT at pH 2.0 and F-400 at pH 8.0, which were attributed to the highly available contact surfaces and molecular sieving, respectively. Its hybrid characteristics incorporating a considerable portion of mesopores and micropores made hypercross linked MN-202 a superior antibiotic adsorbent with high adsorption capacity. Furthermore, the adsorption capacity of MWCNT on the basis of surface area was more advantageous than that of the other adsorbents because MWCNT has a much more compact molecular arrangement.     

Activated carbon adsorption of quinolone antibiotics in water: Performance, mechanism, and modeling

The extensive use of antibiotics has led to their presence in the aquatic environment, and introduces potential impacts on human and ecological health. The capability of powdered activated carbon(PAC) to remove six frequently used quinolone(QN) antibiotics during water treatment was evaluated to improve drinking water safety. The kinetics of QN adsorption by PAC was best described by a pseudo second-order equation, and the adsorption capacity was well described by the Freundlich isotherm equation. Isotherms measured at different p H showed that hydrophobic interaction, electrostatic interaction,and π–π dispersion force were the main mechanisms for adsorption of QNs by PAC. A p H-dependent isotherm model based on the Freundlich equation was developed to predict the adsorption capacity of QNs by PAC at different p H values. This model had excellent prediction capabilities under different laboratory scenarios. Small relative standard derivations(RSDs), i.e., 0.59%–0.92% for ciprofloxacin and 0.09%–3.89% for enrofloxacin,were observed for equilibrium concentrations above the 0.3 mg/L level. The RSDs increased to 11.9% for ciprofloxacin and 32.1% for enrofloxacin at μg/L equilibrium levels, which is still acceptable. This model could be applied to predict the adsorption of other chemicals having different ionized forms.     

Simultaneous removal of dissolved organic matter and bromide from drinking water source by anion exchange resins for controlling disinfection by-products

Anion exchange resins （AERs） with different properties were evaluated for their ability to remove dissolved organic matter （DOM） and bromide, and to reduce disinfection by-product （DBP） formation potentials of water collected from a eutrophic surface water source in Japan. DOM and bromide were simultaneously removed by all selected AERs in batch adsorption experiments. A polyacrylic magnetic ion exchange resin （MIEX） showed faster dissolved organic carbon （DOC） removal than other AERs because it had the smallest resin bead size. Aromatic DOM fractions with molecular weight larger than 1600 Da and fluorescent organic fractions of fulvic acid- and humic acid-like compounds were efficiently removed by all AERs. Polystyrene AERs were more effective in bromide removal than polyacrylic AERs. This result implied that the properties of AERs, i.e. material and resin size, influenced not only DOM removal but also bromide removal efficiency, MIEX showed significant chlorinated DBP removal because it had the highest DOC removal within 30 rain, whereas polystyrene AERs efficiently removed brominated DBPs, especially brominated trihalomethane species. The results suggested that, depending on source water DOM and bromide concentration, selecting a suitable AER is a key factor in effective control of chlorinated and brominated DBPs in drinking water.     

Removal of antibiotics in a parallel-plate thin-film-photocatalytic reactor: Process modeling and evolution of transformation by-products and toxicity

Photocatalytic degradation of sulfamethoxazole(SMX) antibiotic has been studied under recycling batch and homogeneous flow conditions in a thin-film coated immobilized system namely parallel-plate(PPL) reactor. Experimentally designed, statistically evaluated with a factorial design(FD) approach with intent to provide a mathematical model takes into account the parameters influencing process performance. Initial antibiotic concentration, UV energy level, irradiated surface area, water matrix(ultrapure and secondary treated wastewater) and time, were defined as model parameters. A full of 2~5 experimental design was consisted of 32 random experiments. PPL reactor test experiments were carried out in order to set boundary levels for hydraulic, volumetric and defined defined process parameters. TTIP based thin-film with polyethylene glycol + TiO_2 additives were fabricated according to pre-described methodology. Antibiotic degradation was monitored by High Performance Liquid Chromatography analysis while the degradation products were specified by LC–TOF-MS analysis. Acute toxicity of untreated and treated SMX solutions was tested by standard Daphnia magna method. Based on the obtained mathematical model, the response of the immobilized PC system is described with a polynomial equation. The statistically significant positive effects are initial SMX concentration,process time and the combined effect of both, while combined effect of water matrix and irradiated surface area displays an adverse effect on the rate of antibiotic degradation by photocatalytic oxidation. Process efficiency and the validity of the acquired mathematical model was also verified for levofloxacin and cefaclor antibiotics. Immobilized PC degradation in PPL reactor configuration was found capable of providing reduced effluent toxicity by simultaneous degradation of SMX parent compound and TBPs.     

A comparative study and evaluation of sulfamethoxazole adsorption onto organo-montmorillonites

Three organo-montmorillonites were prepared using surfactants, and their adsorption behaviors toward sulfamethoxazole（SMX） were investigated. The surfactants used were cetyltrimethyl ammonium bromide（CTMAB）, 3-（N,N-dimethylhexadecylammonio） propane sulfonate（HDAPS） and 1,3-bis（hexadecyldimethylammonio）-propane dibromide（BHDAP）. The properties of the organo-montmorillonites were characterized by X-ray diffraction, scanning electron microscopy and N2adsorption–desorption isotherm measurements. Results showed that the interlayer spacing of montmorillonite was increased and the surface area as well as the morphology were changed. Batch adsorption experiments showed that the surfactant loading amount had a great effect on the adsorption of SMX. The adsorption process was p H dependent and the maximum adsorption capacity was obtained at p H 3 for HDAPS-Mt, while CTMAB-Mt and BHDAP-Mt showed a high removal efficiency at 3–11. The adsorption capacity increased with the initial SMX concentration and contact time but decreased with increasing solution ionic strength.Kinetic data were best described by the pseudo second-order model. Equilibrium data were best represented by the Langmuir model, and the Freundlich constant（n） indicated a favorable adsorption process. The maximum adsorption capacity of SMX was 235.29 mg/g for CTMAB-Mt, 155.28 mg/g for HDAPS-Mt and 242.72 mg/g for BHDAP-Mt. Thermodynamic parameters were calculated to evaluate the spontaneity and endothermic or exothermic nature. The adsorption mechanism was found to be dominated by electrostatic interaction,while hydrophobic interaction played a secondary role.     

Selection of magnetic anion exchange resins for the removal of dissolved organic and inorganic matters

Four magnetic anion exchange resins (MAERs) were used as adsorbents to purify drinking water. The effect of water quality (pH, temperature, ionic strength, etc.) on the performance of MAER for the removal of dissolved organic matter (DOM) was also investigated. Among the four studied MAERs, the strong base resin named NDMP-1 with high water content and enhanced exchange capacity exhibited the highest removal rate of dissolved organic carbon (DOC) (48.9% removal rate) and UV-absorbing substances (82.4% removal rate) with a resin dose of 10 mL/L after 30 min of contact time. The MAERs could also effectively remove inorganic matter such as sulfate, nitrate and fluoride. Because of the higher specific UV absorbance (SUVA) value, the DOM in the raw water was found to be removed more effectively than that in the clarified water by NDMP resin. The temperature showed a weak influence on the removal of DOC from 6 to 26℃, while a relatively strong one at 36℃. The removal of DOM by NDMP was also affected to some extent by the pH value. Moreover, increasing the sulfate concentration in the raw water could decrease the removal rates of DOC and UV-absorbing substances.     

Adsorption of 17β-estradiol from aqueous solution by raw and direct/pre/post-KOH treated lotus seedpod biochar

Five biochars derived from lotus seedpod(LSP) were applied to examine and compare the adsorption capacity of 17β-estradiol(E2) from aqueous solution.The effect of KOH activation and the order of activation steps on material properties were discussed.The effect of contact time,initial concentration,p H,ionic strength and humic acid on E2 adsorption were investigated in a batch adsorption process.Experimental results demonstrated that the pseudo second-order model fitted the experimental data best and that adsorption equilibrium was reached within 20 hr.The efficiency of E2 removal increased with increasing E2 concentration and decreased with the increase of ionic strength.E2 adsorption on LSP-derived biochar(BCs) was influenced little by humic acid,and slightly affected by the solution p H when its value ranged from 4.0 to 9.0,but considerably affected at p H 10.0.Low environmental temperature is favorable for E2 adsorption.Chemisorption,π–π interactions,monolayer adsorption and electrostatic interaction are the possible adsorption mechanisms.Comparative studies indicated that KOH activation and the order of activation steps had significant impacts on the material.Post-treated biochar exhibited better adsorption capacity for E2 than direct treated,pretreated,and raw LSP biochar.Pyrolyzed biochar at higher temperature improved E2 removal.The excellent performance of BCs in removing E2 suggested that BCs have potential in E2 treatment and that the biochar directly treated by KOH would be a good choice for the treatment of E2 in aqueous solution,with its advantages of good efficiency and simple technology.     

Synthesis of carbon-coated magnetic nanocomposite (Fe3O4@C) and its application for sulfonamide antibiotics removal from water

The occurrence of antibiotics in the environment has recently raised serious concerns regarding their potential threat to human health and aquatic ecosystem. A new magnetic nanocomposite, Fe304@C （Fe304 coated with carbon）, was synthesized, characterized, and then applied to remove five commonly-used sulfonamides （SAs） from water. Due to its combinational merits of the outer functionalized carbon shell and the inner magnetite core, Fe3O4@C exhibited a high adsorption affinity for selected SAs and a fast magnetic separability. The adsorption kinetics of SAs on Fe304 @ C could be expressed by the pseudo second-order model. The adsorption isotherms were fitted well with the Dual-mode model, revealing that the adsorption process consisted of an initial partitioning stage and a subsequent hole-filling stage. Solution pH exerted a strong impact on the adsorption process with the maximum removal efficiencies （74% to 96%） obtained at pH 4.8 for all selected SAs. Electrostatic force and hydrogen bonding were two major driving forces for adsorption, and electron-donor-acceptor interactions may also make a certain contribution. Because the synthesized Fe304@C showed comprehensive advantages of high adsorptivity, fast magnetic separability, and prominent reusability, it has potential applications in water treatment.     

Adsorption and desorption of Cu(Ⅱ) and Pb(Ⅱ) in paddy soils cultivated for various years in the subtropical China

The adsorption and desorption of Cu(Ⅱ) and Pb(Ⅱ) on upland red soil,and paddy soils which were originated from the upland soil and cultivated for 8,15,35 and 85 years,were investigated using the batch method.The study showed that the organic matter content and cation exchange capacity (CEC) of the soils are important factors controlling the adsorption and desorption of Cu(Ⅱ) and Pb(Ⅱ).The 15-Year paddy soil had the highest adsorption capacity for Pb(Ⅱ),followed by the 35-Year paddy soil.Both the 35-Year paddy soil and 15-Year paddy soil adsorbed more Cu(Ⅱ) than the upland soil and other paddy soils.The 15-Year paddy soils exhibited the highest desorption percentage for both Cu(Ⅱ) and Pb(Ⅱ).These results are consistent with the trend for the CEC of the soils tested.The high soil CEC contributes not only to the adsorption of Cu(Ⅱ) and Pb(Ⅱ) but also to the electrostatic adsorption of the two heavy metals by the soils.Lower desorption percentages for Cu(Ⅱ) (36.7% to 42.2%) and Pb(Ⅱ) (50.4% to 57.9%) were observed for the 85-Year paddy soil.The highest content of organic matter in the soil was responsible for the low desorption percentages for the two metals because the formation of the complexes between the organic matter and the metals could increase the stability of the heavy metals in the soils.     

Comparison of different combined treatment processes to address the source water with high concentration of natural organic matter during snowmelt period

The source water in one forest region of the Northeast China had very high natural organic matter (NOM) concentration and heavy color during snowmelt period. The efficiency of five combined treatment processes was compared to address the high concentration of NOM and the mechanisms were also analyzed. Conventional treatment can hardly remove dissolved organic carbon (DOC) in the source water. KMnO₄ pre-oxidization could improve the DOC removal to 22.0%. Post activated carbon adsorption improved the DOC removal of conventional treatment to 28.8%. The non-sufficient NOM removal could be attributed to the dominance of large molecular weight organic matters in raw water, which cannot be adsorbed by the micropore upon activated carbon. O₃ + activated carbon treatment are another available technology for eliminating the color and UV₂₅₄ in water. However, its performance of DOC removal was only 36.4%, which could not satisfy the requirement for organicmatter. The limited ozone dosage is not sufficient to mineralize the high concentration of NOM. Magnetic ion-exchange resin combined with conventional treatment could remove 96.2% of color, 96.0% of UV₂₅₄ and 87.1% of DOC, enabling effluents to meet the drinking water quality standard. The high removal efficiency could be explained by the negative charge on the surface of NOM which benefits the static adsorption of NOM on the anion exchange resin. The results indicated that magnetic ion-exchange resin combined with conventional treatment is the best available technology to remove high concentration of NOM.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.     

Removal of cadmium using MnO2 loaded D301 resin

MnO2 loaded weak basic anion exchange resin D301 （Anion exchange resin, macroreticular weak basic styrene） as adsorbent has been prepared and applied to the removal of cadmium. The adsorption characteristics have been investigated with respect to effect of pH, equilibrium isotherms, removal kinetic data, and interference of the coexisting ions. The results indicated that the Cd^2＋ could be efficiently removed using MnO2 loaded D301 resin in the pH range of 3-8 from aqueous solutions with the co-existence of high concentration of alkali and alkaline-earth metals ions. The saturate adsorption capacity of the Cd^2＋ was 77.88 mg/g. The adsorption process followed the pseudo first-order kinetics. The equilibrium data obtained in this study accorded excellently with the Langmuir adsorption isotherm.     

Effect of coagulation pretreatment on the fouling of ultrafiltration membrane

The purpose of this study is to understand the effect and mechanism of preventing membrane fouling, by coagulation pretreatment, in terms of fractional component and molecular weight of natural organic matter （NOM）. A relatively higher molecular weight （MW） of hydrophobic compounds was responsible for a rapid decline in the ultrafiltration flux. Coagulation could effectively remove the hydrophobic organics, resulting in the increase of flux. It was found that a lower MW of neutral hydrophilic compounds, which could remove inadequately by coagulation, was responsible for the slow declining flux. The fluxes in the filtration of coagulated water and supernatant water were compared and the results showed that a lower MW of neutral hydrophilic compounds remained in the supernatant water after coagulation could be rejected by a membrane, resulting in fouling. It was also found that the coagulated flocs could absorb neutral hydrophilic compounds effectively. Therefore, with the coagulated flocs formed on the membrane surface, the flux decline could be improved.     

Penetration analysis of elements and bioleaching treatment of spent refractory for recycling

Acidithiobacillus ferrooxidans ATCC23270 and Acidithiobacillus thiooxidans TM-32 were used for bioleaching of spent refractories of aluminium and copper melting furnaces for their recycling.Firstly,penetration of elements into aluminium melting furnace refractory was investigated and it was found that up to 7 cm from surface was contaminated.Comparison on leaching efficiency by the strains ATCC23270 and TM-32 found that the strain ATCC23270 could treat larger amount of the refractories than the strain TM-32 could do.In the experiment of bioleaching of spent refractory aluminium melting furnace by the strain ATCC23270,high leaching efficiency were obtained on Al,Si,and Ca,and extremely low leaching performance was,however,shown on the rest of elements i.e.,Na,Mn,and Zn.Under the strain TM-32 use,relatively high leaching performance was recognized on Al,Si,Ca,Na,Mn,and Zn.In the experiment of bioleaching for spent refractory copper melting furnace,almost the same leaching trends were shown on Cu,Zn,Al,and Si under the strains ACTT23270 and TM-32 uses.     

Simultaneous removal of ammonium and phosphate by zeolite synthesized from coal fly ash as influenced by acid treatment

Zeolite synthesized from fly ash （ZFA） without modification is not efficient for the purification of NH4＋ and phosphate at low concentrations that occur in real effluents, despite the high potential removal capacity. To develop an effective technique to enhance the removal efficiency of ammonium and phosphate at low concentrations, ZFA was modified with acid treatment and the simultaneous removal of ammonium and phosphate in a wide range of concentration was investigated. It was seen that when compared with untreated ZFA, only the treatment by 0.01 mol/L of H2SO4 significantly improved the removal efficiency of ammonium at low initial concentrations. The behavior was well explained by the pH effect. Treatment by more concentrated H2SO4 led to the deterioration of the ZFA structure and a decrease in the cation exchange capacity. Treatment by 0.01 mol/L H2SO4 improved the removal efficiency of phosphate by ZFA at all initial P concentrations, while the treatment by concentrated H2SO4 （≥0.9 mol/L） resulted in a limited maximum phosphate immobilization capacity （PIC）. It was concluded that through a previous mild acid treatment （e.g. 0.01 mol/L of H2SO4）, ZFA can be used in the simultaneous removal of NH4＋ and P at low concentrations simulating real effluent.