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.     

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.     

Size characterization of the associations between carbon nanotubes and humic acids in aqueous media by asymmetrical flow field-flow fractionation combined with multi-angle light scattering

This work focuses on the influence of humic acids (HAs) on the fate of carbon nanotubes (CNTs) in aqueous media. This influence was demonstrated by mixing CNT powder with HAs in aqueous solution in varying concentrations. The aqueous media containing HAs and CNTs were size-characterized by asymmetrical flow field-flow fractionation (AsFlFFF) coupled with multi-angle light scattering (MALS). This coupling yielded information concerning the size distribution of single- and multi-walled CNTs (SWCNTs and MWCNTs) and HAs under different physico-chemical conditions that can occur in environmental water. HAs can disperse individual CNTs in aqueous media. However, the difference in the physical structure between SWCNTs and MWCNTs leads to significant differences in the quantity of HA that can adsorb onto the nanotube surface and in the stability of the CNT/HA complex. Compared with MWCNTs, SWCNTs suspended in HAs are less affected by changing ionic strength with respect to stability and the amount suspended.     

Enhanced bioaccumulation of pentachlorophenol in carp in the presence of multi-walled carbon nanotubes

The impact of suspended particles on the bioavailability of pollutants has long been a controversial topic. In this study, adsorption of pentachlorophenol (PCP) onto a natural suspended particulate matter (SPM) and multi-walled carbon nanotubes (MWCNTs) was studied. Facilitated transports of PCP into carp by SPM and MWCNTs were evaluated by bioaccumulation tests exposing carp (Carassius auratus red var.) to PCP-contaminated water in the presence of SPM and MWCNTs, respectively. Desorption of PCP on SPM and MWCNTs in simulated digested fluids was also investigated. The results demonstrate that MWCNTs (K _F?=?7.99?×?10⁴) had a significantly stronger adsorption capacity for PCP than the SPM (K _F?=?19.0). The presence of SPM and MWCNTs both improved PCP accumulation in the carp during the 21 days of exposure, and the 21 days PCP concentration in the carp was enhanced by 25.9 and 12.8 % than that without particles, respectively. The enhancement in bioaccumulation by MWCNTs was less than that by the SPM. Considerably more PCP was accumulated in the viscera of the fish (BCF?=?519495 for SPM and 148955 for MWCNTs), and the difference in PCP concentrations between different tissues became greater with particles. PCP desorption in the simulated digestive fluids was faster than that in the background solution. Compared to MWCNTs-bound PCP, more SPM-bound PCP was desorbed, and K _F of desorption for SPM was at least 4 orders of magnitude higher than that for MWCNTs, which can explain the greater enhancement in bioaccumulation in the presence of SPM. Particle-bound pollutants might pose more risk than pollutants alone.     

Evaluation of methods to determine adsorption of polycyclic aromatic hydrocarbons to dispersed carbon nanotubes

A number of methods have been reported for determining hydrophobic organic compound adsorption to dispersed carbon nanotubes (CNTs), but their accuracy and reliability remain uncertain. We have evaluated three methods to investigate the adsorption of phenanthrene (a model polycyclic aromatic hydrocarbon, PAH) to CNTs with different physicochemical properties: dialysis tube (DT) protected negligible depletion solid phase microextraction (DT-nd-SPME), ultracentrifugation, and filtration using various types of filters. Dispersed CNTs adhered to the unprotected polydimethylsiloxane (PDMS)-coated fibers used in nd-SPME. Protection of the fibers from CNT adherence was investigated with hydrophilic DT, but high PAH sorption to the DT was observed. The efficiency of ultracentrifugation and filtration to separate CNTs from the water phase depended on CNT physicochemical properties. While non-functionalized CNTs were efficiently separated from the water phase using ultracentrifugation, incomplete separation of carboxyl functionalized CNTs was observed. Filtration efficiency varied with different filter types (composition and pore size), and non-functionalized CNTs were more easily separated from the water phase than functionalized CNTs. Sorption of phenanthrene was high (< 70%) for three of the filters tested, making them unsuitable for the assessment of phenanthrene adsorption to CNTs. Filtration using a hydrophilic polytetrafluoroethylene (PTFE) filter membrane (0.1 μm) was found to be a simple and precise technique for the determination of phenanthrene adsorption to a range of CNTs, efficiently separating all types of CNTs and exhibiting a good and highly reproducible recovery of phenanthrene (82%) over the concentration range tested (70–735 μg/L).

     

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.     

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.     

Adsorption-desorption and leaching of pyraclostrobin in Indian soils

Pyraclostrobin is a new broad-spectrum foliar applied and seed protectant fungicide of the strobilurin group. In this paper, adsorption-desorption of pyraclostrobin has been investigated in three different soils viz. Inceptisol (sandy loam, Delhi), Vertisol (sandy clay, Hyderabad) and Ultisol (sandy clay loam, Thrissur). Effect of organic matter and clay content on sorption was also studied in Inceptisol of Delhi. Leaching potential of pyraclostrobin as influenced by rainfall was studied in intact soil columns to confirm the results of adsorption-desorption studies. The adsorption studies were carried out at initial concentrations of 0.05, 0.1, 0.5, 1 and 1.5 μg mL^?1. The distribution coefficient (K_d) values in three test soils ranged from 4.91 to 18.26 indicating moderate to high adsorption. Among the three test soils, adsorption was the highest in Ultisol (K_d 18.26), followed by Vertisol (K_d 9.87) and Inceptisol (K_d 4.91). K_F value was also highest for Ultisol soil (66.21), followed by Vertisol (40.88) and Inceptisol (8.59). S-type adsorption isotherms were observed in all the three test soils. K_d values in organic carbon-removed soil and clay-removed soil were 3.57 and 2.83 respectively, indicating lower adsorption than normal Inceptisol. Desorption studies were carried out at initial concentrations of 0.5, 1 and 1.5 μg mL^?1. Desorption was the greatest in Inceptisol, followed by Vertisol and Ultisol. Amounts of pyraclostrobin desorbed in three desorption cycles for different concentrations were 23.1–25.3%, 9.4–20.7% and 8.1–13.6% in Inceptisol, Vertisol and Ultisol respectively. Desorption was higher in clay fraction-removed and organic carbonremoved soils than normal Inceptisol. Desorption was slower than adsorption in all the test soils, indicating hysteresis effect (with hysteresis coefficient values varying from 0.05 to 0.20). Low values of hysteresis coefficient suggest high hysteresis effect indicating easy and strong adsorption, and slow desorption, of pyraclostrobin in soils. Higher hysteresis coefficient values in organic carbon removed soil (0.25–0.30) and clay fraction removed soil (0.28–0.36) as compared to normal Inceptisol soil suggest relatively weak adsorption and easy desorption of pyraclostrobin. Results of regression analysis suggest that the organic matter and pH of the soil play a major role in adsorption of pyraclostrobin. Leaching studies were carried out in intact soil columns in Inceptisol. The columns were leached with different amounts of water simulating different amounts of rainfall. The results suggest that most of the pyraclostrobin residues will remain present in the top soil layers even under high rainfall conditions and chances of pyraclostrobin moving to lower soil depth are almost negligible.     

CdS-TiO_2/MWCNTs结构表征及其光催化性能

采用溶胶-凝胶法,制备了多壁碳纳米管(MWCNTs)负载的双组分复合半导体光催化剂CdS-TiO2/MWCNTs。通过透射电镜(TEM)、比表面分析(BET)、X射线衍射(XRD)和紫外-可见吸收光谱(UV-vis)等分析方法对光催化剂进行了结构表征,并考察了CdS-TiO2/MWCNTs对甲苯降解的光催化性能。结果表明:纳米活性粒子CdS-TiO2均匀负载于MWCNTs上,比表面积、光吸收阈值和强度增大,活性粒子间以及活性粒子与载体之间具有协同作用,有利于光催化性能的提高,CdS-TiO2/MWCNTs在主波长为254 nm紫外光照射下对甲苯的降解效果较好,去除率可达55.3%。     

CdS-TiO2/MWCNTs结构表征及其光催化性能

采用溶胶-凝胶法,制备了多壁碳纳米管（MWCNTs）负载的双组分复合半导体光催化剂CdS-TiO2/MWCNTs。通过透射电镜（TEM）、比表面分析（BET）、X射线衍射（XRD）和紫外-可见吸收光谱（UV-vis）等分析方法对光催化剂进行了结构表征,并考察了CdS-TiO2/MWCNTs对甲苯降解的光催化性能。结果表明：纳米活性粒子CdS-TiO2均匀负载于MWCNTs上,比表面积、光吸收阈值和强度增大,活性粒子间以及活性粒子与载体之间具有协同作用,有利于光催化性能的提高,CdS-TiO2/MWCNTs在主波长为254 nm紫外光照射下对甲苯的降解效果较好,去除率可达55.3%。     

Adsorption of sulfamethoxazole on functionalized carbon nanotubes as affected by cations and anions

The environmental risks of antibiotics have attracted lots of research attention, but their environmental behavior is not clear yet. Functionalized carbon nanotubes (CNTs) were used as model adsorbents and sulfamethoxazole (SMX) was used as a model antibiotic to investigate the effect of both cations (Ca²⁺, Cs⁺) and anions (phosphate) on antibiotics adsorption. Various mechanisms (such as electrostatic interaction, hydrophobic interaction, π-π and hydrogen bonds) play roles in SMX adsorption. Cations and anions could “wedge into” these mechanisms and thus alter SMX adsorption. This study emphasized that both increased and decreased SMX adsorption could be observed with the addition of cations/anions, depending on environmental conditions (such as pH in this current study). The net effect is the balance between the increased and decreased effects. The contribution of different mechanisms to the overall antibiotic adsorption on solid particles should be identified to accurately predict the apparent effect by cations and anions.     

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.     

Sorption behavior of a new acidic herbicide in soils

The sorptive behavior of the experimental herbicide quinmerac (7-chloro-3-methyl-quinoline-8-carboxylic acid) was investigated in soils of different organic carbon content. Distribution coefficients are low (K_d = 0.03 - 12 mL g⁻¹) and are mainly determined by the soil organic carbon content. The adsorption mechanism operating in neutral to slightly acid agricultural soils is supposed to be cation bridging with the anionic form of quinmerac. Under acid conditions (pH 5.2) the predominating sorption mechanism is hydrophobic interaction. Therefore soil pH and cationic composition are also major factors determining the sorptive capacity of soils for quinmerac.

Adsorption kinetics, equilibrium adsorption and desorption isotherms were determined in batch experiments. Sorption kinetics were investigated at various times from 15 min to 96 hours. A two-step sorption behavior with time was found for the anionic form indicating two types of sorption mechanisms or sorption sites. Equilibrium for the first type was reached at a time-scale of minutes and for the second type after 24 hours. Adsorption isotherms were determined for two soil/solution ratios 1/5 and 1/3. Alteration of the adsorbent concentration exerted a strong influence on the adsorption isotherms. An increase of sorption was found with increasing adsorbent concentration. Under natural soil conditions sorption is therefore expected to be higher compared to the batch experiments. Desorption isotherms were obtained using the consecutive desorption method. Desorption hysteresis was not observed which indicates weak interactions. Implications of the results for the movement of quinmerac under field conditions and for models describing transport are discussed.     

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...     

Synthesis of hybrid carbon nanotubes using Brassica juncea L. application to photodegradation of bisphenol A

Hyperaccumulators contain tubular cellulose and heavy metals, which can be used as the sources of carbon and metals to synthesize nanomaterials. In this paper, carbon nanotubes (CNTs), Cu_0.05Zn_0.95O nanoparticles, and CNTs/Cu_0.05Zn_0.95O nanocomposites were synthesized using Brassica juncea L. plants, and the ultraviolet (UV)-light-driven photocatalytic degradations of bisphenol A (BPA) using them as photocatalysts were studied. It was found that the outer diameter of CNTs was around 50 nm and there were a few defects in the crystal lattice. The synthesized Cu_0.05Zn_0.95O nanocomposites had a diameter of around 40 nm. Cu_0.05Zn_0.95O nanocomposites have grown on the surface of the CNTs and the outer diameter of them was around 100 nm. The synthesized hybrid carbon nanotubes using B. juncea could enhance the efficiency of photocatalytic degradation on BPA. The complete equilibration time of adsorption/desorption of BPA onto the surface of CNTs, Cu_0.05Zn_0.95O nanoparticles, and CNTs/Cu_0.05Zn_0.95O nanocomposites was within 30, 20, and 30 min, and approximately 14.9, 8.7, and 17.4 % BPA was adsorbed by them, respectively. The combination of UV light irradiation (90 min) with CNTs, Cu_0.05Zn_0.95O nanoparticles, and CNTs/Cu_0.05Zn_0.95O nanocomposites could lead to 48.3, 75.7, and 92.6 % decomposition yields of BPA, respectively. These findings constitute a new insight for synthesizing nanocatalyst by reusing hyperaccumulators.     

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.     

Adsorption properties of kaolinite-based nanocomposites for Fe and Mn pollutants from aqueous solutions and raw ground water: kinetics and equilibrium studies

Raw kaolinite was used in the synthesis of metakaolinite/carbon nanotubes (K/CNTs) and kaolinite/starch (K/starch) nanocomposites. Raw kaolinite and the synthetic composites were characterized using XRD, SEM, and TEM techniques. The synthetic composites were used as adsorbents for Fe and Mn ions from aqueous solutions and natural underground water. The adsorption by the both composites is highly pH dependent and achieves high efficiency within the neutral pH range. The experimental adsorption data for the uptake of Fe and Mn ions by K/CNTs were found to be well represented by the pseudo-second-order kinetic model rather than the intra-particle diffusion model or Elovich model. For the adsorption using K/starch, the uptake results of Fe ions was well fitted by the second-order model, whereas the uptake of Mn ions fitted well to the Elovich model rather than pseudo-second-order and intra-particle diffusion models The equilibrium studies revealed the excellent fitting of the removal of Fe and Mn ions by K/CNTs and Fe using K/starch with the Langmuir isotherm model rather than with Freundlich and Temkin models. But the adsorption of Mn ions by K/starch is well fitted with Freundlich rather than Temkin and Langmuir isotherm models. The thermodynamic studies reflected the endothermic nature and the exothermic nature for the adsorption by K/CNTs and K/starch nanocomposites, respectively. Natural ground water contaminated by 0.4 mg/L Fe and 0.5 mg/L Mn was treated at the optimum conditions of pH 6 and 120 min contact time. Under these conditions, 92.5 and 72.5% Fe removal efficiencies were achieved using 20 mg of K/CNTs and K/starch nanocomposites, respectively. Also, K/CNTs nanocomposite shows higher efficiency in the removal of Mn ions as compared to K/starch nanocomposite.     

The adverse effects of injected functionalized multi-walled carbon nanotube (f-MWCNT) on in vivo neurosecretory brain cells of Jamaican field cricket,Gryllus assimilis

Environmental Science and Pollution Research - Carbon nanotubes (CNTs) have been increasingly more prevalent due to their use in product technology owing to their exceptional electrical and thermal...