Effect of pH and the role of organic matter in the adsorption of isoproturon on soils

Equilibrium measurements were carried out with the herbicide isoproturon on natural adsorbents (brown forest-, chernozem-, sandy soils and quartz) in different buffered media (pH 5, 7, 8 phosphate buffer). Adsorption isotherms were fitted by a multi-step adsorption equation providing numerical information used in the environmental propagation models and risk assessment works. In the adsorption of the slightly polar isoproturon the dissolved organic matter of the soil and the pH play an important role. At molecular level, results are interpreted by taking into consideration the hydrophobic interaction and the formation of hydrogen bonds between the surface and the solute. The observed adsorption behavior indicates that the organic matter content of the soils and its soluble fulvic acid, alkaline soluble humic acid and insoluble humin fractions were considerable different. The chernozem soil containing the highest amount of insoluble organic fraction proved to be a very efficient adsorbent. The brown forest and the sandy soils exhibit rather similar adsorbent properties but at pH 7 the latter containing more fulvic acid adsorbs less isoproturon due to the enhanced solubility of the soil organic matter. In alkaline conditions the negatively charged solute and the surface repel each other and the hydrophobic interactions are also weaker than in neutral media.     

Role of surface functionality in the adsorption of anionic dyes on modified polymeric sorbents

While synthetic polymeric sorbents effectively treat dye wastewaters by adsorption, the underlying mechanisms remain to be understood. This work determined the adsorption of an anionic dye by three polymers differing significantly in surface functionality. Surface functional groups of polymers were indicated in FTIR spectra and quantified by the Boehm titration. In reference to the commercial sorbent XAD-4 with a low degree of functionality, the laboratory synthesized NG-8 had primarily acidic functional groups, whereas its aminated product MN-8 had mainly basic amino groups. Electrophoresis determined the points of zero charge of 4.18, 3.23, and 4.51 for XAD-4, NG-8, and MN-8, respectively. The adsorption of Reactive Black 5 dye (RB5) by all the sorbents on a unit surface area basis increased with decreasing pH. At the same low pH (4.40), the adsorption by NG-8 was similar to that by XAD-4, indicating little influence of protonated (neutral) surface functional groups. In contrast, the adsorption by NG-8 at pH 6.05 was 75% lower than that by XAD-4, resulting apparently from the strong electrostatic repulsion between RB5 and deprotonated (negative) groups. Amination substantially enhanced RB5 adsorption by eliminating acidic groups and creating a positive charge on the surface of MN-8. The adsorptive enhancement was also achieved in the presence of CaCl2, due presumably to the neutralization of negative surface charge by Ca2+ and the RB5-Ca2+ pairing. These results manifest the important role of surface functionality in the adsorption of dyes by synthetic polymers.     

Adsorption of pharmaceutical compounds and an endocrine disruptor from aqueous solutions by carbon materials

Adsorption has been used to study the removal of atenolol, caffeine, diclofenac and isoproturon, pharmaceutical compounds as emerging contaminants and an endocrine disruptor from ultrapure water and a municipal wastewater treatment plant effluent with three carbonaceous materials: activated carbon, multiwalled carbon nanotubes and carbon nanofibers. The adsorption capacities were studied in the temperature range of 25-65°C and pH range from 3 to 9. Several model isotherms were used to model the adsorption equilibrium data. Also, the competitive adsorption was evaluated.     

Removal of sulfamethoxazole from solution by raw and chemically treated walnut shells

Purpose

The sorption of sulfamethoxazole, a frequently detected pharmaceutical compound in the environment, onto walnut shells was evaluated.

Methods

The sorption proprieties of the raw sorbent were chemically modified and two additional samples were obtained, respectively HCl and NaOH treated. Scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric (TG/DTG) techniques were applied to investigate the effect of the chemical treatments on the shell surface morphology and chemistry. Sorption experiments to investigate the pH effect on the process were carried out between pH?2 and 8.

Results

The chemical treatment did not substantially alter the structure of the sorbent (physical and textural characteristics) but modified the surface chemistry of the sorbent (acid?Cbase properties, point of zero charge??pH_pzc). The solution pH influences both the sorbent??s surface charge and sulfamethoxazole speciation. The best removal efficiencies were obtained for lower pH values where the neutral and cationic sulfamethoxazole forms are present in the solution. Langmuir and Freundlich isotherms were applied to the experimental adsorption data for sulfamethoxazole sorption at pH?2, 4, and 7 onto raw walnut shell. No statistical difference was found between the two models except for the pH?2 experimental data to which the Freundlich model fitted better.

Conclusion

Sorption of sulfamethoxazole was found to be highly pH dependent in the entire pH range studied and for both raw and treated sorbent.     

流动注射分光光度法研究离子强度对活性炭吸附阴、阳离子染料的影响

运用流动注射分光光度法,考察了不同离子强度(NaCl)下,在水溶液中表面带负电的活性炭分别吸附阴、阳离子染料的动力学行为。实验结果表明,对于所考察的2种阳离子染料和3种阴离子染料,活性炭的表观吸附速率常数均随着离子强度的增大而增大。这种加速吸附效应的出现,主要是因为离子强度的增大促进了活性炭表面与染料之间的非静电力作用。     

The Emergence of Black Carbon as a Super-Sorbent in Environmental Chemistry: The End of Octanol?

The distribution of aromatic contaminants between environmental solids and water solution reflects both absorption by the organic matrix (organic carbon, OC) and adsorption to black carbon (BC). In many instances, adsorption to BC dominates the interaction between aromatic contaminants and environmental solids. This holds especially true for the pyrogenically produced PAHs and PCDD/Fs, but also for the industrially produced PCBs and PCNs. In the future, research will need to surface-normalize the adsorption onto BC surfaces. One of the key questions to be addressed is the relative distribution and availability of contaminants associated with OC and BC fractions in environmental solids.     

Influence of anionic, cationic and nonionic surfactants on adsorption and desorption of oxytetracycline by ultrasonically treated and non-treated multiwalled carbon nanotubes

High adsorption capacity of carbon nanotubes (CNTs) may greatly determine the bioavailability and mobility of organic contaminants. The fate of contaminants adsorbed by CNTs may be substantially influenced by surfactants used both in the synthesis and dispersion of CNTs. The aim of this research was to determine the influence of surfactants (nonionic - TX100, cationic - CTAB and anionic - SDBS) on adsorption and desorption of oxytetracycline (OTC) by multiwalled carbon nanotubes (MWCNTs). The surfactants used had a substantial influence on both adsorption and desorption of OTC. The direction of changes depended clearly on the type of surfactant. In case of anionic SDBS, increased adsorption of OTC by MWCNTs was observed. The presence of TX100 and CTAB decreased the adsorption of OTC by MWCNTs significantly. The increase of OTC adsorption after ultrasonic treatment was observed in case of MWCNTs alone and MWCNTs with SDBS and TX100. However, ultrasonic treatment caused OTC adsorption decrease in the presence of CTAB. The change of pH had also an important effect on OTC adsorption in the presence of surfactants. Depending on the surfactant and pH, an increase or decrease of OTC adsorption was observed. The presence of surfactants increased OTC desorption from MWCNTs significantly as follows: SDBS = CTAB < TX100. The results obtained suggest new potential threats and constitute a basis for further research considering the bioavailability and toxicity of antibiotics in the presence of MWCNTs and surfactants.     

Investigating the sources of the mutagenic activity found in a river using the Salmonella assay and different water extraction procedures

In the routine São Paulo state (Brazil) surface water quality-monitoring program, which includes the Salmonella microsome mutagenicity assay as one of its parameters, a river where water is taken and treated for drinking water purposes has repeatedly shown mutagenic activity. A textile dyeing facility employing azo-type dyes was the only identifiable source of mutagenic compounds. We extracted the river and drinking water samples with XAD4 at neutral and acidic pH and with blue rayon, which selectively adsorbs polycyclic compounds. We tested the industrial effluent, raw, and treated water and sediment samples with YG1041 and YG1042 and compared the results with the TA98 and TA100 strains. The elevated mutagenicity detected with YG-strains suggested that nitroaromatics and/or aromatic amines were causing the mutagenicity detected in the samples analyzed. Positive responses for the blue rayon extracts indicated that mutagenic polycyclic compounds were present in the water samples analyzed. The mutagen or mixture of mutagens present in the effluent and water samples cause mainly frameshift mutations and are positive with and without metabolic activation. The Salmonella assay combined with different extraction procedures proved to be very useful in the identification of the origin of the pollution and in the identification of the classes of chemical compounds causing the mutagenic activity in the river analyzed.     

pH-Dependent fate and transport of NTA-complexed cobalt through undisturbed cores of fractured shale saprolite

The codisposal of toxic metals and radionuclides with organic chelating agents has been implicated in the facilitated transport of the inorganic contaminants away from primary waste disposal areas. We investigated the transport of Co(II)NTA through undisturbed cores of fractured shale saprolite. Experiments were conducted across the pH range 4 to 8 by collecting cores from different locations within the weathering profile. Aqueous complexation, adsorption, dissociation and oxidation reactions influenced Co(II)NTA transport. The suite of reaction products identified in column effluent varied with experimental pH. At low pH and in the presence of abundant exchangeable aluminum, Co transport occurred predominantly as the Co2+ ion. At higher pH, Co was transported primarily as Co(II)NTA and the Co(III) species Co(III)(HNTA)2 and Co(III)(IDA)2. The formation of the geochemical oxidation products (Co(III) species) has far reaching implications as these compounds are kinetically and thermodynamically stable, are transported more rapidly than Co(II)NTA, and are resistant to biodegradation. These results demonstrate that natural minerals, in the physical structure encountered naturally, can be more important in the formation of mobile, stable contaminant forms than they can be for the retardation and dissociation of the contaminants.     

Application of molecularly imprinted and non-imprinted polymers for removal of emerging contaminants in water and wastewater treatment: a review

Over the past decade, several studies have reported trace levels of endocrine disrupting compounds, pharmaceuticals, and personal care products in surface waters, drinking water, and wastewater effluents. There has also been an increased concern about the ecological and human health impact of these contaminants, and their removal from water and wastewater has become a priority. Traditional treatment processes are limited in their ability to remove emerging contaminants from water, and there is a need for new technologies that are effective and feasible. This paper presents a review on recent research results on molecularly imprinted (MIP) and non-imprinted (NIP) polymers and evaluates their potential as a treatment method for the removal of emerging contaminants from water and wastewater. It also discusses the relative benefits and limitations of using MIP or NIP for water and wastewater treatment. MIP, and in particular NIP, offer promising applications for wastewater treatment, but their toxicity and possible health effects should be carefully studied before they are considered for drinking water treatment. More research is also required to determine how best to incorporate MIP and NIP in treatment plants.     

A holistic passive integrative sampling approach for assessing the presence and potential impacts of waterborne environmental contaminants

As an integral part of our continuing research in environmental quality assessment approaches, we have developed a variety of passive integrative sampling devices widely applicable for use in defining the presence and potential impacts of a broad array of contaminants. The semipermeable membrane device has gained widespread use for sampling hydrophobic chemicals from water and air, the polar organic chemical integrative sampler is applicable for sequestering waterborne hydrophilic organic chemicals, the stabilized liquid membrane device is used to integratively sample waterborne ionic metals, and the passive integrative mercury sampler is applicable for sampling vapor phase or dissolved neutral mercury species. This suite of integrative samplers forms the basis for a new passive sampling approach for assessing the presence and potential toxicological significance of a broad spectrum of environmental contaminants. In a proof-of-concept study, three of our four passive integrative samplers were used to assess the presence of a wide variety of contaminants in the waters of a constructed wetland, and to determine the effectiveness of the constructed wetland in removing contaminants. The wetland is used for final polishing of secondary-treatment municipal wastewater and the effluent is used as a source of water for a state wildlife area. Numerous contaminants, including organochlorine pesticides, polycyclic aromatic hydrocarbons, organophosphate pesticides, and pharmaceutical chemicals (e.g., ibuprofen, oxindole, etc.) were detected in the wastewater. Herein we summarize the results of the analysis of the field-deployed samplers and demonstrate the utility of this holistic approach.     

Partitioning and removal of dioxin-like congeners in flue gases treated with activated carbon adsorption

Activated carbon adsorption is commonly used to control dioxin-like congener (PCDD/Fs and PCBs) emissions. Partitioning of PCDD/Fs and PCBs between vapor and solid phases and their removal efficiencies achieved with existing air pollution control devices (APCDs) at a large-scale municipal waste incinerator (MWI) and an industrial waste incinerator (IWI) are evaluated via intensive stack sampling and analysis. Those two facilities investigated are equipped with activated carbon injection (ACI) with bag filter (BF) and fixed activated carbon bed (FACB) as major PCDD/F control devices, respectively. Average PCDD/F and PCB concentrations of stack gas with ACI+BF as APCDs are 0.031 and 0.006ng-TEQ/Nm(3), and that achieved with FACB are 1.74 and 0.19ng-TEQ/Nm(3) in MWI and IWI, respectively. The results show that FACB could reduce vapor-phase PCDD/Fs and PCBs concentrations in flue gas, while the ACI+BF can effectively adsorb the vapor-phase dioxin-like congener and collect the solid-phase PCDD/Fs and PCBs in the meantime. Additionally, the results of the pilot-scale adsorption system (PAS) experimentation indicate that each gram activated carbon adsorbs 105-115ng-PCDD/Fs and each surface area (m(2)) of activated carbon adsorbs 10-25ng-PCDD/Fs. Based on the results of PAS experimentation, this study confirms that the surface area of mesopore+macropore (20-200A) of the activated carbon is a critical factor affecting PCDD/F adsorption capacity.     

Trimethylphenylammonium-smectite as an effective adsorbent of water soluble aromatic hydrocarbons

Homoionic trimethylphenylammonium (TMPA)- and tetramethylammonium (TMA)-clays were prepared by ion-exchange reactions using two smectite clays that differed in their cation exchange capacities and surface charge densities. These clays are referred to as a low-charge (SAC) and high-charge (SWa)-smectite. The organo-clays were evaluated as adsorbents of water soluble aromatic hydrocarbons including benzene, toluene, ethylbenzene, p-xylene, butylbenzene, and naphthalene. All of the aromatic hydrocarbons tested were effectively removed from water by the low-charge TMPA-smectite. The low-charge TMA-smectite was an effective adsorbent for benzene but was ineffective in the removal of the alkylbenzenes and naphthalene from water. The effect of surface charge on the adsorption properties of TMPA-smectite was pronounced. The uptake of benzene and toluene by the high-charge TMPA-smectite was greatly reduced as compared to the low-charge TMPA-smectite. These results suggest the utility of TMPA-smectite as a liner material for petroleum storage containers and waste disposal reservoirs. The use of TMPA-smectite in conjunction with Na-smectite would provide a barrier with the ability to impede the flow of water and to effectively adsorb dissolved organic contaminants.     

Trimethylphenylammonium-Smectite as an Effective Adsorbent of Water Soluble Aromatic Hydrocarbons

Homoionic trimethylphenylammonium (TMPA)- and tetramethylammonium (TMA)-clays were prepared by Ion-exchange reactions using two smectite clays that differed in their cation exchange capacities and surface charge densities. These clays are referred to as a low-charge (SAC) and high-charge (SWa)-smectite. The organo-clays were evaluated as adsorbents of water soluble aromatic hydrocarbons including benzene, toluene, ethylbenzene, p-xylene, butylbenzene, and naphthalene. All of the aromatic hydrocarbons tested were effectively removed from water by the low-charge TMPA-smectite. The low-charge TMA-smectite was an effective adsorbent for benzene but was ineffective in the removal of the alkylbenzenes and naphthalene from water. The effect of surface charge on the adsorption properties of TMPA-smectite was pronounced. The uptake of benzene and toluene by the high-charge TMPA-smectite was greatly reduced as compared to the low-charge TMPAsmectite. These results suggest the utility of TMPA-smectite as a liner material for petroleum storage containers and waste disposal reservoirs. The use of TMPA-smectite in conjunction with Na-smectite would provide a barrier with the ability to impede the flow of water and to effectively adsorb dissolved organic contaminants.     

负载TiO_2的活性炭纤维改性电极电吸附除氟

采用溶胶-凝胶法制备TiO2凝胶,将TiO2凝胶涂覆在活性炭纤维表面并进行热处理制备改性电极（TiO2/ACF）,利用扫描电子显微镜（SEM）、X射线衍射光谱仪（XRD）、比表面和孔隙度分析仪对负载前后电极的表面特性进行表征,并探讨了其对NaF溶液的电吸附效果。结果表明,电极负载TiO2后表面变得粗糙,比表面积和总孔体积减小,而介孔体积和平均孔径增大。此外,表面的TiO2同时以金红石和锐钛矿的晶型存在。电吸附实验结果显示,加电可以提高吸附容量,而且电压、pH和初始氟离子浓度均对电吸附容量产生影响：电压增大,吸附容量增加,当施加电压为2 V时,电吸附容量为1.03 mg/g,比开路电位时提高40%;pH可以通过影响氟离子在溶液中的存在形态和TiO2/ACF电极表面的羟基基团对电吸附容量产生影响;初始氟离子浓度升高,电极吸附容量增大,但是去除率降低。在处理初始氟离子浓度为4 mg/L的NaF溶液时,在2 V电压、中性pH和12 h的吸附时间下,改性ACF为电极的吸附量为1.32 mg/g。     

Characterization of an adsorbed humin-like substance on an allophanic soil formed via catalytic polycondensation between catechol and glycine, and its adsorption capability to pentachlorophenol

An allophanic soil (AS) catalyzed the formation of dark-colored polymers via polycondensation reactions between catechol and glycine. The organic carbon content of the AS was increased from 0.16% to 1.3%, indicating that some of the dark-colored polymers had been adsorbed to the AS. The characteristics of the dark-colored polymers adsorbed on the AS were similar to those of a humin that is not extractable with an aqueous alkaline solution. Such a humin-like substance (HuLS) was separated from the AS by treatment with a mixture of HF and HCl. The HuLS and humic acid-like substance (HaLS), comprising the acid-insoluble fraction in the reaction mixture, were characterized by elemental analysis, size exclusion chromatography, pyrolysis-GC/MS and ¹³C NMR. However, the structural features of HaLS and HuLS had many points in common. These results suggest that HuLS-AS can be regarded as an organo-clay complex formed by the strong adsorption of HaLS to the AS. The adsorption of pentachlorophenol (PCP) to AS and HuLS-AS was examined at pH 5.5. At this pH, the zeta potential of the HuLS-AS showed a negative value. It would, therefore, be expected that pentachlorophenolate anions would adsorb with difficulty to HuLS-AS because of electrostatic repulsion. Nevertheless, the adsorption coefficient for PCP to HuLS-AS, as estimated by the Freundlich isotherm, was seven times larger than that for AS. These results show that HuLS, when adsorbed on the AS surface, has the capability to enhance the adsorption of PCP.     

反应柱充填活性炭法处理轧钢含铬废水的研究

针对轧钢含铬废水,分别采用活性炭和离子交换树脂吸附处理的方法对其中的Cr^6＋和Cr^3＋的去除效果进行了系统的研究。静态试验考查了pH、吸附剂用量和搅拌速度等因素的影响,同时使用微型反应柱集成装置对穿透时间、吸附容量及活性炭再生方法进行了探讨,动态试验表明反应柱充填活性炭法能有效地处理含铬废水。     

铁盐改性砂制备及其吸附Zn~(2+)的性能研究

通过改变石英砂表面的物理化学性质,提高石英砂的吸附效率,考察其对废水中的Zn~(2+)去除效果.以石英砂为载体,分别用反复高温加热法和反复碱性沉积法制备了三氯化铁改性砂、硝酸铁改性砂,测定2种方法制备的铁盐改性砂的表面含铁量、铁盐的酸稳定性及比表面积,并比较2种铁盐改性砂对Zn~(2+)的吸附效果.结果表明,三氯化铁改性砂、硝酸铁改性砂的比表面积分别为2.468、4.247 m~2/g,比石英砂比表面积分别提高6.910、12.612倍;在pH为中性条件下,石英砂对Zn~(2+)去除率为43%左右,三氯化铁改性砂对Zn~(2+)去除率达到70%左右,硝酸铁改性砂对Zn~(2+)去除率达到85%左右,表明铁盐改性砂对Zn~(2+)去除能力比石英砂有很大提高;铁盐改性砂对Zn~(2+)的吸附有一定容量,表面的活性中心越多,吸附能力越大;铁盐改性砂对Zn~(2+)的去除率随着pH的升高而增加,当pH>8.5时,Zn~(2+)去除率可达90%左右.     

氧化/吸附/混凝协同工艺处理焦化废水生物处理出水的过程及效果分析

针对焦化废水生物处理出水中继续存在多种有机污染物而影响达标及存在安全隐患的现状,基于废水中有机物的物理化学特性,构建了氧化/吸附/混凝的深度处理过程。在NaC lO投加量为40 mg/L,AC投加量为500 mg/L,PFS投加量为300 mg/L,反应时间为0.5 h,以及pH为7.0的最佳条件下,先氧化后吸附混凝,该过程可以实现COD去除率为75%以上,色度去除率80%以上,处理后的水样其COD值与色度值分别下降到60 mg/L及20倍以下;通过GC/MS方法分析处理前后水样中的有机物组分,发现水样中大部分单环芳香族化合物和多环芳香族化合物,部分含氮杂环化学物、有机氯化物以及溴化物被去除,但是,长链烷烃和部分芳香烃继续保留。研究结果证明了氧化/吸附/混凝协同工艺的效果与焦化废水生物出水中有机污染物的分子结构、存在形态形成构效关系,催化作用与氧化作用的协同是获得高效去除率的关键。     

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.