Aqueous suspensions of carbon nanotubes: Surface oxidation, colloidal stability and uranium sorption

The objective of this study is to obtain information on the behaviour of carbon nanotubes (CNTs) as potential carriers of pollutants in the case of accidental CNT release to the environment and on the properties of CNTs as a potential adsorbent material in water purification. The effects of acid treatment of CNTs on (i) the surface properties, (ii) the colloidal stability and (iii) heavy metal sorption are investigated, the latter being exemplified by uranium(VI) sorption. There is a pronounced influence of surface treatment on the behaviour of the CNTs in aqueous suspension. Results showed that acid treatment increases the amount of acidic surface groups on the CNTs. Therefore, acid treatment has an increasing effect on the colloidal stability of the CNTs and on their adsorption capacity for U(VI). Another way to stabilise colloids of pristine CNTs in aqueous suspension is the addition of humic acid.     

Cadmium (Cd2+) removal by nano zerovalent iron: surface analysis, effects of solution chemistry and surface complexation modeling

Nano zerovalent iron (nZVI) is an effective remediant for removing various organic and inorganic pollutants from contaminated water sources. Batch experiments were conducted to characterize the nZVI surface and to investigate the effects of various solution properties such as pH, initial cadmium concentration, sorbent dosage, ionic strength, and competitive ions on cadmium removal by nZVI. Energy-dispersive X-ray and X-ray photoelectron spectroscopy results confirmed removal of Cd²⁺ ions by nZVI through adsorption. Cd²⁺ adsorption decreased in the presence of competitive cations in the order: Zn²⁺?>?Co²⁺?>?Mg²⁺?>?Mn²⁺?=?Cu²⁺?>?Ca²⁺?>?Na²⁺?=?K⁺. Higher concentrations of Cl^? significantly decreased the adsorption. Cadmium removal increased with solution pH and reached a maximum at pH 8.0. The effects of various solution properties indicated Cd²⁺ adsorption on nZVI to be a chemisorption (inner-sphere complexation) process. The three surface complexation models (diffuse layer model, constant capacitance model, and triple layer model) fitted well to the adsorption edge experimental data indicating the formation of nZVI–Cd bidentate inner-sphere surface complexes. Our results suggest that nZVI can be effectively used for the removal of cadmium from contaminated water sources with varying chemical conditions.     

碳纳米管对水中多氯联苯的吸附动力学

通过静态吸附实验研究了碳纳米管（CNTs）对水中多氯联苯（PCBs）的吸附动力学特性,包括1种单壁碳纳米管（SWCNTs）和3种多壁碳纳米管（MWCNTs）,并对4种CNTs的物理特征及孔径分布进行了分析。结果表明,SWCNTs的比表面积和总孔容最大,分别为228.210 m2·g-1和1.515 4 cm3·g-1。CNTs对PCBs的吸附速率很快,40 min吸附量可达到平衡时的90%以上,80 min左右达到吸附平衡,且SWCNTs的吸附能力远大于MWCNTs。运用拟一级和拟二级动力学模型对实验数据进行拟合,表明拟二级模型更适合描述CNTs对PCBs的吸附过程。     

Different stabilities of multiwalled carbon nanotubes in fresh surface water samples

The stability of multiwalled carbon nanotubes (MWNTs) in particulate aggregates and surfactant-facilitated suspensions after being mixed into eight types of fresh surface water samples was investigated. MWNTs in particulate aggregates could not be stabilized in any of the water samples except for the one having relatively high content of dissolved organic matter with the aid of sonication. Sodium dodecyl benzenesulfonate (SDBS), polyethylene glycol octylphenyl ether (TX100) and cetyltrimethyl ammonium bromide (CTAB) were used to prepare MWNT suspensions. SDBS- and TX100-stabilized MWNTs could partly remain suspending after being mixed into the water samples, whereas CTAB-stabilized MWNTs readily sedimentated due to the surface charge neutralization by the surface water contained negatively-charged anions and colloids. This is a first systematic study examining the stability of carbon nanotubes in natural surface waters, the results from which will be useful for understanding the transport, fate and ecological effect of carbon nanotubes in the aqueous environment.     

Oxidized multiwalled carbon nanotubes as adsorbent for the removal of manganese from aqueous solution

A batch adsorption process was applied to investigate the removal of manganese from aqueous solution by oxidized multiwalled carbon nanotubes (MWCNTs). In doing so, the thermodynamic, adsorption isotherm, and kinetic studies were also carried out. MWCNT with 5–10-nm outer diameter, surface area of 40–600 m²/g, and purity above 95 % was used as an adsorbent. A systematic study of the adsorption process was performed by varying pH, ionic strength, and temperature. Manganese-adsorbed MWCNT was characterized by Raman, FTIR, X-ray diffraction, XPS, SEM, and TEM. The adsorption efficiency could reach 96.82 %, suggesting that MWCNT is an excellent adsorbent for manganese removal from water. The results indicate that second-order kinetics model was well suitable to model the kinetic adsorption of manganese. Equilibrium data were well described by the typical Langmuir adsorption isotherm. Thermodynamic studies revealed that the adsorption reaction was spontaneous and endothermic process. The experimental results showed that MWCNT is an excellent manganese adsorbent. The MWCNTs removed the manganese present in the water and reduced it to a permissible level making it drinkable.     

表面改性活性炭对水中头孢拉定的吸附性能

为了研究改性前后活性炭对水中低浓度头孢拉定的吸附效果,探讨了投加量、初始浓度、温度、pH值和时间对吸附去除率的影响。结果表明,经Fe(NO3)3溶液改性后,活性炭对头孢拉定的吸附能力得到加强;经Fe(NO3)3溶液浸渍改性获得的活性炭对头孢拉定的吸附,能很好地与Langmuir型等温方程拟合,线性相关数达0.98以上;吸附过程符合二级反应动力学描述,线性相关数达0.998以上。     

三氯生在碳纳米管上的吸附

药品和个人护理用品(PPCPs)已成为一个引起广泛关注的新的环境问题。采用碳纳米管（CNTs）对水溶液中的三氯生进行吸附处理,考察了碳纳米管粒径及用量、温度、pH、振荡时间等因素对三氯生去除率的影响。研究结果表明,碳纳米管能快速吸附水中的三氯生,粒径较小的碳纳米管可获得较高的三氯生去除率;低温有利于吸附反应的进行;pH在6.5～7.0时,三氯生的去除率可达97%。三氯生在碳纳米管上的吸附可以很好地用Langmuir和Freundlich吸附等温方程进行描述。     

Adsorption of microcystins by carbon nanotubes

The production of cyanobacterial toxins microcystins (MCs) by cyanobacterial bloom which may promote the growth of tumor in human liver is a growing environmental problem worldwide. In this paper, the adsorption of MC-RR and LR, which were extracted from cyanobacterial cells in Dianchi Lake in China, by carbon nanotubes (CNTs), wood-based activated carbon (ACs) and clays were investigated. Compared with ACs and clay materials of sepiolite, kaolinite and talc tested, CNTs were found to have a strong ability in the adsorption of MCs. At the concentrations of 21.5 mg l(-1) MC-RR and 9.6 mg l(-1) MC-LR in 50 mmol phosphate buffer solution (pH 7.0), the adsorption amounts of MCs by CNTs with the range of outside diameter from 2 to 10nm were 14.8 and 5.9 mg g(-1), which were about four times higher than those by other adsorbents tested. It was shown that with the decrease of CNTs outside diameters from 60 to 2 nm, the adsorption amount of MCs was apparently increased, however the size of CNTs particles formed in solution declined. This result implies that the size of CNTs tube pore that is fit for the molecular dimension of MCs plays a dominant role. Furthermore the specific surface area of CNTs was also found to be a factor in the adsorption of MCs. The results suggested that the selection of suitable size of CNTs as a kind of adsorbent is very important in the efficient eliminating MCs from drinking water in future.     

Combined effects of carbon nanotubes and cadmium on the photosynthetic capacity and antioxidant response of wheat seedlings

Environmental Science and Pollution Research - A detailed study of nanomaterials has revealed their broad application prospects. However, the presence of carbon nanotubes (CNTs) in the environment...     

Degradation of carbon tetrachloride by iron metal: Complexation effects on the oxide surface

Dehalogenation of chlorinated aliphatic contaminants at the surface of zero-valent iron metal (Fe⁰) is mediated by the thin film of iron (hydr)oxides found on Fe⁰ under environmental conditions. To evaluate the role this oxide film plays in the reduction of chlorinated methanes, carbon tetrachloride (CCl₄) degradation by Fe⁰ was studied under the influence of various anions, ligands, and initial CCl₄ concentrations ([P]_o). Over the range of conditions examined in these batch experiments, the reaction kinetics could be characterized by surface-area-normalized rate constants that were pseudo-first order for CCl₄ disappearance (k_CCl4), and zero order for the appearance of dissolved Fe²⁺ (k_Fe²⁺). The rate of dechlorination exhibits saturation kinetics with respect to [P]_o, suggesting that CCl₄ is transformed at a limited number of reactive surface sites. Because oxidation of Fe⁰ by CCl₄ is the major corrosion reaction in these systems, k_Fe²⁺ also approaches a limiting value at high CCl₄ concentrations. The adsorption of borate strongly inhibited reduction of CCl₄, but a concomitant addition of chloride partially offset this effect by destabilizing the film. Redox active ligands (catechol and ascorbate), and those that are not redox active (EDTA and acetate), all decreased k_CCl4 (and k_Fe²⁺). Thus, it appears that the relatively strong complexation of these ligands at the oxide–electrolyte interface blocks the sites where weak interactions with the metal oxide lead to dehalogenation of chlorinated aliphatic compounds.     

Aqueous carbonation of peridotites for carbon utilisation: a critical review

Environmental Science and Pollution Research - Peridotite and serpentinites can be used to sequester CO2 emissions through mineral carbonation. Olivine dissolution rate is directly proportional...     

Investigation of solution chemistry effects on sorption behavior of Cu(II) on ZSM-5 zeolite

The sorption of Cu(II) from an aqueous solution using ZSM-5 zeolite was investigated by batch technique under ambient conditions. Sorption was investigated as a function of pH, ionic strength, foreign ions, humic substances, and temperature. The results indicate that the sorption of Cu(II) on ZSM-5 zeolite is strongly dependent on pH. Sorption is dependent on ionic strength at low pH, but independent of ionic strength at high pH values. The presence of humic/fluvic acid (HA/FA) enhances the sorption of Cu(II) on ZSM-5 zeolite at low pH values, and reduces Cu(II) sorption at high pH values. Sorption isotherms were well simulated by the Langmuir model. Thermodynamic parameters (i.e., deltaH0, deltaS0 and deltaG0) for the sorption of Cu(II) were determined from temperature-dependent sorption isotherms at 293.15, 313.15, and 333.15 K, respectively. Results indicate that the sorption process of Cu(II) on ZSM-5 zeolite is spontaneous and endothermic.     

Coupled effects of solution chemistry and hydrodynamics on the mobility and transport of quantum dot nanomaterials in the vadose zone

To investigate the coupled effects of solution chemistry and hydrodynamics on the mobility of quantum dot (QD) nanoparticles in the vadose zone, laboratory scale transport experiments involving single and/or sequential infiltrations of QDs in unsaturated and saturated porous media, and computations of total interaction and capillary potential energies were performed. As ionic strength increased, QD retention in the unsaturated porous media increased; however, this retention was significantly suppressed in the presence of a non-ionic surfactant in the infiltration suspensions as indicated by surfactant enhanced transport of QDs. In the vadose zone, the non-ionic surfactant limited the formation of QD aggregates, enhanced QD mobility and transport, and lowered the solution surface tension, which resulted in a decrease in capillary forces that not only led to a reduction in the removal of QDs, but also impacted the vadose zone flow processes. When chemical transport conditions were favorable (ionic strength of 5 × 10(-4)M and 5 × 10(-3)M, or ionic strengths of 5 × 10(-2)M and 0.5M with surfactant), the dominating phenomena controlling the mobility and transport of QDs in the vadose zone were meso-scale processes, where infiltration by preferential flow results in the rapid transport of QDs. When chemical transport conditions were unfavorable (ionic strength of 5 × 10(-2)M and 0.5M) the dominating phenomena controlling the mobility and transport of QDs in the vadose zone were pore-scale processes governed by gas-water interfaces (GWI) that impact the mobility of QDs. The addition of surfactant enhanced the transport of QDs both in favorable and unfavorable chemical transport conditions. The mobility and retention of QDs was controlled by interaction and capillary forces, with the latter being the most influential. GWI were found to be the dominant mechanism and site for QD removal compared with solid-water interfaces (SWI) and pore straining. Additionally, ripening phenomena were demonstrated to enhance QDs removal or retention in porous media and to be attenuated by the presence of surfactant.     

改进碳纳米管/聚氨酯复合材料吸附硝基苯

以酸化碳纳米管(CNTs)强化聚氨酯泡沫(PUF),通过原位聚合法制备碳纳米管/聚氨酯复合材料(CPUF)。借助红外光谱(FT-IR)、扫描电镜(SEM)、热失重分析(TGA)和力学性能测试等方法研究和表征了CPUF复合材料的性能和结构。研究了用CPUF复合材料对人工模拟废水中硝基苯(NB)的吸附性能、影响因素及其再生后吸附效果。结果表明,CPUF复合材料对硝基苯具有较强的吸附能力,在p H=5.4、投加量为2 g/L、接触时间24 h的条件下,升高温度会降低CPUF复合材料的饱和吸附量,但会提高初始吸附速率,等温吸附过程符合Langmuir方程,属于单分子吸附。饱和后的复合材料可采用简单热再生,再生后对NB的吸附能力没有明显下降。     

黑炭负载零价铁对复合污染土壤中铜和铬的稳定化效果及生物有效性影响

采用直接热解法和碳热还原法分别制备了黑炭(BC)和黑炭负载零价铁(BF)材料,通过土壤稳定化培养实验和盆栽实验,考察了BC和BF对复合污染土壤中铜和铬的稳定化效果及其对生物有效性的影响。实验结果表明,BC可提高土壤pH,BF则降低土壤的pH。在投加量为5 g·kg-1的情况下,处理30 d后,BC和BF对土壤中TCLP-Cu的去除率分别为76.99%和69.83%;BC对TCLP-Crtotal和TCLP-Cr(VI)去除率分别为91.07%和92.47%,BF对TCLP-Crtotal和TCLP-Cr(VI)的去除率均接近100%,两者均能有效降低土壤重金属迁移性。形态分析表明,投加BC和BF均促进了铜由酸可提取态向可还原态和可氧化态转化,同时使铬的酸可提取态降低,可氧化态增加。盆栽实验表明,BC和BF均大大降低了土壤中铜和铬的生物有效性,减弱了其由植物根部向地上迁移的能力。相比而言,BF在对复合污染土壤中铜和铬的稳定化效果、形态转化以及迁移性方面整体优于BC。     

Investigation of the effects of using single-wall carbon nanotubes (SWCNTs) in ozone measurement with passive samplers

Passive samplers are used in air quality monitoring for many years to compete in terms of being economical with continuous measurement systems. In this study, different amounts of single-wall carbon nanotubes (SWCNTs) were added in the impregnation solution of the filters of passive samplers and the effect on the absorption of ozone studied. The results of the measurement of ozone with varying amounts of SWCNTs added to the impregnation solution of the filters of the passive samplers were compared with the results of the continuous ozone measurement system (CS). Measurements were performed for 7 days and 14 days at two different exposure times. The increase of the amount of SWCNTs on the filters of the passive samplers, however, did not have an effect on the measurement of ozone. The measurement results of the passive samplers of the 14-day exposure periods, alternating with the 7-day exposure periods, were lower considerably than the results of the 7-day exposure.

Implications: The accuracy and the use of passive samplers in SWCNTs are expected to provide high measurement results. Observing the effect of the change in the amount of diffusion of pollutants held in the SWCNT is also one of the expected implications.     

Effect of multiwalled carbon nanotubes on UASB microbial consortium

The continuous rise in production and applications of carbon nanotubes (CNTs) has grown a concern about their fate and toxicity in the environment. After use, these nanomaterials pass through sewage and accumulate in wastewater treatment plants. Since, such plants rely on biological degradation of wastes; their activity may decrease due to the presence of CNTs. This study investigated the effect of multiwalled carbon nanotubes (MWCNTs) on upflow anaerobic sludge blanket (UASB) microbial activity. The toxic effect on microbial viability, extracellular polymeric substances (EPS), volatile fatty acids (VFA), and biogas generation was determined. The reduction in a colony-forming unit (CFU) was 29 and 58 % in 1 and 100 mg/L test samples, respectively, as compared to control. The volatile fatty acids and biogas production was also found reduced. The scanning electron microscopy (SEM) and fluorescent microscopy images confirmed that the MWCNT mediated microbial cell damage. This damage caused the increase in EPS carbohydrate, protein, and DNA concentration. Fourier transform infrared (FTIR) spectroscopy results supported the alterations in sludge EPS due to MWCNT. Our observations offer a new insight to understand the nanotoxic effect of MWCNTs on UASB microflora in a complex environment system.