Removal of sulfamethoxazole and sulfapyridine by carbon nanotubes in fixed-bed columns

Sulfamethoxazole (SMX) and sulfapyridine (SPY), two representative sulfonamide antibiotics, have gained increasing attention because of the ecological risks these substances pose to plants, animals, and humans. This work systematically investigated the removal of SMX and SPY by carbon nanotubes (CNTs) in fixed-bed columns under a broad range of conditions including: CNT incorporation method, solution pH, bed depth, adsorbent dosage, adsorbate initial concentration, and flow rate. Fixed-bed experiments showed that pH is a key factor that affects the adsorption capacity of antibiotics to CNTs. The Bed Depth Service Time model describes well the relationship between service time and bed depth and can be used to design appropriate column parameters. During fixed-bed regeneration, small amounts of SMX (3%) and SPY (9%) were irreversibly bonded to the CNT/sand porous media, thus reducing the column capacity for subsequent reuse from 67.9 to 50.4 mg g^?1 for SMX and from 91.9 to 72.9 mg g^?1 for SPY. The reduced column capacity resulted from the decrease in available adsorption sites and resulting repulsion (i.e., blocking) of incoming antibiotics from those previously adsorbed. Findings from this study demonstrate that fixed-bed columns packed with CNTs can be efficiently used and regenerated to remove antibiotics from water.     

Testing the resistance of single- and multi-walled carbon nanotubes to chemothermal oxidation used to isolate soots from environmental samples

Quantification of natural and engineered carbon nanotubes (CNT) in the environment is urgently needed to study their occurrence and fate and to enable a proper risk assessment. Currently, such methods are lacking. Here, we tested the resistance of 15 structurally different CNTs to chemothermal oxidation at 375 °C (CTO-375), a method used to isolate soots from environmental samples. Depending on their structure, CNTs survived CTO-375 in proportions ranging from 26 to 93%. Standard addition of CNTs to soil and sediment yielded recoveries between 66 and 171%, demonstrating the capability of CTO-375 to isolate CNTs from complex environmental matrices. These data of pure and added CNTs correspond to recoveries obtained with “ordinary” soots under similar experimental conditions. Hence, soot fractions commonly isolated with CTO-375 from environmental matrices most probably encompass CNTs. Future work should attempt to enhance the method's selectivity, i.e., its capability to separate CNTs from other forms of soot.     

Remediation of phenanthrene-contaminated soil by simultaneous persulfate chemical oxidation and biodegradation processes

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous compounds with carcinogenic and/or mutagenic potential. To address the limitations of individual remediation techniques and to achieve better PAH removal efficiencies, the combination of chemical and biological treatments can be used. The degradation of phenanthrene (chosen as a model of PAH) by persulfate in freshly contaminated soil microcosms was studied to assess its impact on the biodegradation process and on soil properties. Soil microcosms contaminated with 140 mg/kg_{DRY SOIL} of phenanthrene were treated with different persulfate (PS) concentrations 0.86–41.7 g/kg_{DRY SOIL} and incubated for 28 days. Analyses of phenanthrene and persulfate concentrations and soil pH were performed. Cultivable heterotrophic bacterial count was carried out after 28 days of treatment. Genetic diversity analysis of the soil microcosm bacterial community was performed by PCR amplification of bacterial 16S rDNA fragments followed by denaturing gradient gel electrophoresis (DGGE). The addition of PS in low concentrations could be an interesting biostimulatory strategy that managed to shorten the lag phase of the phenanthrene biological elimination, without negative effects on the physicochemical and biological soil properties, improving the remediation treatment.     

Passive water sampling for polynuclear aromatic hydrocarbons using lipidcontaining semipermeable membrane devices (SPMDs): Application to contaminant residence times

Lipid-containing semipermeable membrane devices are applied to the quantitative determination of the persistence of polynuclear aromatic hydrocarbons (PAH) in an irrigation water canal, a representative waterway. The uniform and reproducible sampling of the USGS design of lipid-containing SPMDs is exploited to measure PAH half-lives without requiring calculation of water concentrations. The trend in calculated PAH half-lives agrees with that expected if volatilization is a significant mechanism for loss from the canal with more volatile PAHs having shorter half-lives. The higher persistence of phenanthrene compared to anthracene is consistent with the greater stability of phenanthrene and suggests, with other physicochemical evidence, that other (reactive) mechanisms may be involved. The results of this study demonstrate the feasibility of the SPMD method for the measurement of residence times in aquatic and other compartments. Such information is essential for quantifying contaminant behavior in the environment and providing insights into contaminant fate.     

有机粘土矿物对水中低浓度菲的吸附性能和机理

分别选用十六烷三甲基溴化铵(HDTMA-Br)、四甲基溴化铵(TMA-Br)、聚乙二醇(PEG)表面活性剂改性天然粘土矿物,研究其对水中低浓度多环芳烃类难降解有机物菲的吸附性能和机理,并讨论了有机粘土的用量对吸附菲的性能的影响,验证了有机粘土矿物吸附菲后的稳定性.3种有机粘土矿物对菲的吸附等温线均呈中凹型,表现为分配系数(Kp)逐渐增大,表明吸附是分配作用和溶剂化效应共同作用的结果.根据Kp及土样有机碳含量(foc)所得的经有机碳归一化的分配系数(Koc)基本为常数,远远高于天然土壤/沉积物的Koc.在相同实验条件下,3种有机粘土矿物中HDTMA改性粘土矿物对菲的吸附性能最强,PEG改性粘土矿物次之,TMA改性粘土矿物最差.     

Contribution of sugar-cane harvesting season to atmospheric contamination by polycyclic aromatic hydrocarbons (PAHs) in Araraquara city,Southeast Brazil

In Brazil, sugar-cane crops are burned to facilitate harvesting, and this causes environmental pollution from the large amounts of smoke and soot that are released into the atmosphere. The smoke and soot contain numerous organic compounds such as PAHs. In this study, PM₁₀ and PAH concentrations in the air of Araraquara (SE Brazil, with around 200,000 inhabitants and surrounded by sugar-cane plantations) were determined during the harvest and non-harvest seasons. The sampling strategy included two campaigns in each season, with 20 samples per season. PM₁₀ was collected using a Hi-vol sampler with Teflon? – coated glass fiber filters. PM₁₀ ranged from 41 to 181 μg m^?3 during the harvest season, and from 12 to 47 μg m^?3 during the non-harvest season. The mean total concentration of PAHs was 2.5 ng m^?3 (non-harvest season) and 11.6 ng m^?3 (harvest season). In all sampling periods, the most abundant polycyclic aromatic hydrocarbons were phenanthrene and fluoranthrene, and the least abundant was anthracene. The cluster analysis of the total PAH concentrations for each day of sampling and the corresponding meteorological data suggested that the atmospheric concentration of PAHs was independent of the differences in the weather between the seasons. For both sampling seasons, the statistical treatment (PCA, Varimax rotation and HCA) indicated the presence of vehicle sources (diesel, gasoline, and natural-gas engines); but for the harvest season, the main source was attributed to sugar-cane burning. The data generated by this study indicated the burning of sugar-cane as the main contributor to the high levels of PAHs detected in samples during the sugar-cane harvest season.     

Desorption of polycyclic aromatic hydrocarbons from carbon nanomaterials in water

Desorption behavior of pyrene, phenanthrene and naphthalene from fullerene, single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs) was examined. Available adsorption space of carbon nanotubes (CNTs) was found to be the cylindrical external surface, neither the inner cavities nor inter-wall spaces due to impurities in the CNTs and restricted spaces (0.335nm) of the MWCNTs, respectively. Desorption hysteresis was observed for fullerene but not for CNTs. Deformation-rearrangement was proposed to explain the hysteresis of polycyclic aromatic hydrocarbons (PAHs) for fullerene, due to the formation of closed interstitial spaces in spherical fullerene aggregates. However, long, cylindrical carbon nanotubes could not form such closed interstitial spaces in their aggregates due to their length, thus showing no significant hysteresis. High adsorption capacity and reversible adsorption of PAHs on CNTs imply the potential release of PAHs if PAH-adsorbed CNTs are inhaled by animals and humans, leading to a high environmental and public health risk.     

Influence of a large steel complex on the spatial distribution of volatile polycyclic aromatic hydrocarbons (PAHs) determined by passive air sampling using membrane-enclosed copolymer (MECOP)

Membrane-enclosed copolymer (MECOPs) samplers containing crystalline copolymers of ethylvinylbenzene-divinylbenzene in polyethylene membranes were used to assess the influence of a steel complex on the level and spatial distribution of polycyclic aromatic hydrocarbons (PAHs) in ambient air. MECOPs were deployed at six sites in Pohang, Korea for 37 days (August 9, 2005–September 14, 2005). Fluorene, phenanthrene, anthracene, and fluoranthene were dominant PAHs with the highest contribution of phenanthrene (59%) to the total amount of vapor-phase PAHs. The spatial distribution of total PAHs in the vapor phase ranging from 76 to 1077 ng MECOP⁻¹ and air dispersion modeling suggested that the steel complex was the major PAH source in Pohang. It was revealed that the major wind directions rather than the distance from the steel complex were a significant factor affecting the levels of PAHs at the sampling sites. Finally, we tried to convert MECOP concentrations (ng MECOP⁻¹) to air concentrations (ng m⁻³) with the modified sampling rates (m³ day⁻¹). This study demonstrates again that passive air samplers are useful tools for spatially resolved and time-integrated monitoring of semivolatile organic compounds (SOCs) in ambient air.     

Removal of carbon nanotubes from aqueous environment with filter paper

The potential health and environmental hazards of carbon nanotubes (CNTs) have been a concerned issue. However, in contrast to the wide recognition of the toxicity of CNTs, little attention has been paid to the decontamination/remediation of CNT pollution. In this study, we report that CNTs can be removed from aqueous environment. In the presence of Ca²⁺, CNTs aggregate quickly to micron size and then enable easy and effective removal via normal filtration. After filtration, CNT suspension becomes colorless with the remnant CNT concentration less than 0.5 μg mL⁻¹, a safe dose based on the published data. The filtration approach also works well in the presence of typical surfactant and dissolved organic matter. The removal efficiency is Ca²⁺ concentration-dependent and regulated by the initial pH value and ionic strength. Our study is helpful for future decontamination of CNTs from aqueous environment.     

Single walled carbon nanotube reactivity and cytotoxicity following extended aqueous exposure

Globally carbon nanoparticles are increasingly utilized, yet it is not known if these nanoparticles pose a threat to the environment or human health. This investigation examined ‘as-prepared’, and acid cleaned carbon nanoparticle physicochemical characteristics (by FTIR, TEM, FESEM, UV-VIS and X-ray microanalysis), and whether these characteristics changed following 2.5-7 yr exposure to pH neutral saline or fresh water. To determine if these aqueous aged nanotubes were cytotoxic, these nanotubes were incubated with human epithelial monolayers and analyzed for cell viability (vital staining) and ultrastructural nanoparticle binding/localization (TEM, FESEM). The presence of Ni and Y catalyst, was less damaging to cells than CNT lattice surface oxidation. Extended fresh water storage of oxidized CNTs did not reduce surface reactive groups, nor lessen cell membrane destruction or cell death. However storing oxidized CNTs in saline or NOM significantly reduced CNT-induced cell membrane damage and increased cell survival to control levels.     

Atmospheric polycyclic aromatic hydrocarbons observed over the North Pacific Ocean and the Arctic area: Spatial distribution and source identification

During the 2003 Chinese Arctic Research Expedition from the Bohai Sea to the high Arctic (37–80°N) aboard the icebreaker Xuelong (Snow Dragon), air samples were collected using a modified high-volume sampler that pulls air through a quartz filter and a polyurethane foam plug (PUF). These filters and PUFs were analyzed for particulate phase and gas phase polycyclic aromatic hydrocarbons (PAHs), respectively, in the North Pacific Ocean and adjacent Arctic region. The ∑PAHs (where ∑=15 compounds) ranged from undetectable level to 4380 pg m⁻³ in the particulate phase and 928–92 600 pg m⁻³ in the gas phase, respectively. A decreasing latitudinal trend was observed for gas-phase PAHs, probably resulting from temperature effects, dilution and decomposition processes; particulate-phase PAHs, however, showed poor latitudinal trends, because the effects of temperature, dilution and photochemistry played different roles in different regions from middle-latitude source areas to the high latitudes. The ratios of PAH isomer pairs, either conservative or sensitive to degradation during long-range transport, were employed to interpret sources and chemical aging of PAHs in ocean air. In this present study the fluoranthene/pyrene and indeno[123-cd]pyrene/benzo[ghi]pyrene isomer pairs, whose ratios are conservative to photo-degradation, implies that biomass or coal burning might be the major sources of PAHs observed over the North Pacific Ocean and the Arctic region in the summer. The isomer ratios of 1,7/(1,7+2,6)-DMP (dimethylphenanthrene) and anthracene/phenanthrene, which are sensitive to aging of air masses, not only imply chemical evolving of PAHs over the North Pacific Ocean were different from those over the Arctic, but reveal that PAHs over the Arctic were mainly related to coal burning, and biomass burning might have a larger contribution to the PAHs over the North pacific ocean.     

Effect of humic acids on physicochemical property and Cd(II) sorption of multiwalled carbon nanotubes

Carbon nanotubes (CNTs), as a type of superior adsorbents for both organic and inorganic contaminants, are increasingly introduced into the environment. Ubiquitous natural organic matter (NOM) would coat on the released CNTs and change their physicochemical properties and sorption of contaminants. The effects of four sequentially extracted humic acids (HAs, as a model NOM) from a peat soil on the physicochemical properties and Cd(II) sorption of three multiwalled CNTs (MWNTs) with different surface areas were investigated. The MWNTs as purchased with very few oxygen-containing functional groups had relatively low sorption capacities (0.93–1.49 mg g⁻¹) for Cd(II) and the sorption capacity increased with increasing surface area of the MWNTs. Surface-coating with the HAs lowered surface areas of the MWNTs but greatly increased their sorption capacities (5.42–18.4 mg g⁻¹). The MWNT-bound HAs introduced oxygen-containing functional groups and negative charges to the MWNT surfaces, which could thus increase the apparent sorption of Cd(II) through chemical complexation and electrostatic attraction, respectively. The later-extracted HAs with lower polarity were more favorable for the surface-coating but increased less Cd(II) sorption by the MWNTs. The results are expected to shed light on understanding the underlying mechanism of the effect of NOM on the sorption of heavy metal ions by CNTs.     

SARA Title III,Section 313 —Looking Ahead

This study performed a workplace evaluation of emission control using available air sampling filters and characterized the emitted particles captured in filters. Characterized particles were contained in the exhaust gas released from carbon nanotube (CNT) synthesis using chemical vapor deposition (CVD). Emitted nanoparticles were collected on grids to be analyzed using transmission electron microscopy (TEM). CNT clusters in the exhaust gas were collected on filters for investigation. Three types of filters, including Nalgene surfactant-free cellulose acetate (SFCA), Pall A/E glass fiber, and Whatman QMA quartz filters, were evaluated as emission control measures, and particles deposited in the filters were characterized using scanning transmission electron microscopy (STEM) to further understand the nature of particles emitted from this CNT production. STEM analysis for collected particles on filters found that particles deposited on filter fibers had a similar morphology on all three filters, that is, hydrophobic agglomerates forming circular beaded clusters on hydrophilic filter fibers on the collecting side of the filter. CNT agglomerates were found trapped underneath the filter surface. The particle agglomerates consisted mostly of elemental carbon regardless of the shapes. Most particles were trapped in filters and no particles were found in the exhaust downstream from A/E and quartz filters, while a few nanometer-sized and submicrometer-sized individual particles and filament agglomerates were found downstream from the SFCA filter. The number concentration of particles with diameters from 5 nm to 20 µm was measured while collecting particles on grids at the exhaust piping. Total number concentration was reduced from an average of 88,500 to 700 particle/cm³ for the lowest found for all filters used. Overall, the quartz filter showed the most consistent and highest particle reduction control, and exhaust particles containing nanotubes were successfully collected and trapped inside this filter.

Implications: As concern for the toxicity of engineered nanoparticles grows, there is a need to characterize emission from carbon nanotube synthesis processes and to investigate methods to prevent their environmental release. At this time, the particles emitted from synthesis were not well characterized when collected on filters, and limited information was available about filter performance to such emission. This field study used readily available sampling filters to collect nanoparticles from the exhaust gas of a carbon nanotube furnace. New agglomerates were found on filters from such emitted particles, and the performance of using the filters studied was encouraging in terms of capturing emissions from carbon nanotube synthesis.     

An integrated approach to understanding the sorption mechanism of phenanthrene by cork

Previous studies have shown the high sorption affinity of polycyclic aromatic hydrocarbons by cork. The aim of the present work is to go further by investigating the sorption mechanism of polycyclic aromatic hydrocarbons (exemplified by phenanthrene) on cork and the availability of the chemical components (i.e. lignin, suberin, holocellulose and extractives) to retain phenanthrene.Two approaches were integrated to reach this objective: (1) statistical multivariate analysis to obtain correlations between the sorption capacity, measured as K_oc, and the sorbent properties (i.e. polarity, acidic functional groups, %dichloromethane extractives, %ethanol and water extractives, %suberin, %lignin and %holocellulose) and (2) modeling calculations to obtain information on interaction at the molecular level.The statistical multivariate analysis demonstrated a strong and positive correlation between K_oc and the lignin content as well as negative correlations between K_oc and the phenolic groups and %dichloromethane extractives contents. The modeling study showed that the lignin–phenanthrene interaction is mostly hydrophobic in nature being largely determined by the π-stacking interaction between the aromatic groups of the interacting partners. This result justifies the observed correlations as dichloromethane extractives, being hydrophobic, compete with phenanthrene adsorption, whereas phenolic groups, as well as negatively charged groups, enhance the hydrophilic character of the sorbent surface, thus hindering the adsorption of phenanthrene.     

Correlations of Eisenia fetida metabolic responses to extractable phenanthrene concentrations through time

Eisenia fetida earthworms were exposed to phenanthrene for thirty days to compare hydroxypropyl-β-cyclodextrin (HPCD) extraction of soil and ¹H NMR earthworm metabolomics as indicators of bioavailability. The phenanthrene 28-d LC₅₀ value was 750 mg/kg (632-891, 95% confidence intervals) for the peat soil tested. The initial phenanthrene concentration was 319 mg/kg, which biodegraded to 16 mg/kg within 15 days, at which time HPCD extraction suggested that phenanthrene was no longer bioavailable. Multivariate statistical analysis of ¹H NMR spectra for E. fetida tissue extracts indicated that phenanthrene exposed and control earthworms differed throughout the 30 day experiment despite the low phenanthrene concentrations present after 15 days. This metabolic response was better correlated to total phenanthrene concentrations (Q² = 0.59) than HPCD-extractable phenanthrene concentrations (Q² = 0.46) suggesting that ¹H NMR metabolomics offers considerable promise as a novel, molecular-level method to directly monitor the bioavailability of contaminants to earthworms in the environment.     

Nonlinear binding of phenanthrene to the extracted fulvic acid fraction in soil in comparison with other organic matter fractions and to the whole soil sample

Fractions of soil organic matter in a natural soil were extracted and sorption (or binding) characteristics of phenanthrene on each fraction and to the whole sample were investigated. The organic carbon normalized single point sorption (or binding) coefficient followed lipid > humin (HM) > humic acid (HA) > fulvic acid (FA) > whole soil sample, while the nonlinear exponent exhibited lipid > FA > HA > whole soil sample > HM. FA showed nonlinear binding of phenanthrene as it often does with other fractions. HM and HA contributed the majority of organic carbon in the soil. The calculated sorption coefficients of the whole soil were about two times greater than the measured values at different equilibrium phenanthrene concentrations. As for phenanthrene, the sorption capacity and nonlinearity of the physically mixed HA-HM mixtures were stronger as compared to the chemically reconstituted HA-HM composite. This was attributed to (besides the conditioning effect of the organic solvents) interactions between HA and HM and acid-base additions during fractionation.     

Air–water exchange fluxes of polycyclic aromatic hydrocarbons in the tropical coast,Taiwan

Air–water exchange fluxes of polycyclic aromatic hydrocarbons (PAHs) were simultaneously measured in air and water samples from two sites on the Kenting coast, located at the southern tip of Taiwan, from January to December 2010. There was no significant difference in the total PAH (t-PAH) concentrations in both gas and dissolved phases between these two sites due to the less local input which also coincided to the low levels of t-PAH concentration; the gas and dissolved phases averaged 1.29 ± 0.59 ng m^?3 and 2.17 ± 1.19 ng L^?1 respectively. The direction and magnitude of the daily flux of PAHs were significantly influenced by wind speed and dissolved PAH concentrations. Individual PAH flux ranged from 627 ng m^?2 d^?1 volatilization of phenanthrene during the rainy season with storm–water discharges raising dissolved phase concentration, to 67 ng m^?2 d^?1 absorption of fluoranthene during high wind speed periods. Due to PAH annual fluxes through air–water exchange, Kenting seawater is a source of low molecular weight PAHs and a reservoir of high molecular weight PAHs. Estimated annual volatilization fluxes ranged from 7.3 μg m^?2 yr^?1 for pyrene to 50 μg m^?2 yr^?1 for phenanthrene and the absorption fluxes ranged from ?2.6 μg m^?2 yr^?1 for chrysene to ?3.5 μg m^?2 yr^?1 for fluoranthene.     

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.     

Nitration of polycyclic aromatic hydrocarbons adsorbed to different carriers in a fluidized bed reactor

The reactivity of selected polycyclic aromatic hydrocarbons (PAH) adsorbed to various surfaces has been studied. PAH were adsorbed to silica, alumina or charcoal particles and exposed to ambient concentrations of NO₂ in air in a fluidized bed reactor. The reaction products were analyzed by capillary gas chromatography and gas chromatograpy/mass spectrometry.The results show that silica is a more reactive surface than alumina. The charcoal used showed to be very adsorbtive and too little material was recovered for analyses. The reactivity of the PAH compounds studied decrease in the order perylene > benzo(a)pyrene > pyrene > chrysene > fluoranthene and phenanthrene. The relevance of these results to the assessment of the possible formation of nitro-PAH in the atmosphere is discussed.     

Anaerobic biodegradation of polycyclic aromatic hydrocarbon in soil

Known concentrations of phenanthrene, pyrene, anthracene, fluorene and acenapthene were added to soil samples to investigate the anaerobic degradation potential of polycyclic aromatic hydrocarbon (PAH). Consortia-treated river sediments taken from known sites of long-term pollution were added as inoculum. Mixtures of soil, consortia, and PAH (individually or combined) were amended with nutrients and batch incubated. High-to-low degradation rates for both soil types were phenanthrene > pyrene > anthracene > fluorene > acenaphthene. Degradation rates were faster in Taida soil than in Guishan soil. Faster individual PAH degradation rates were also observed in cultures containing a mixture of PAH substrates compared to the presence of a single substrate. Optimal incubation conditions were noted as pH 8.0 and 30 degrees C. Degradation was enhanced for PAH by the addition of acetate, lactate, or pyruvate. The addition of municipal sewage or oil refinery sludge to the soil samples stimulated PAH degradation. Biodegradation was also measured under three anaerobic conditions; results show the high-to-low order of biodegradation rates to be sulfate-reducing conditions > methanogenic conditions > nitrate-reducing conditions. The results show that sulfate-reducing bacteria, methanogen, and eubacteria are involved in the PAH degradation; sulfate-reducing bacteria constitute a major component of the PAH-adapted consortia.