Onur G. Apul

Adsorption of aromatic organic contaminants by graphene nanosheets: comparison with carbon nanotubes and activated carbon.

Adsorption of two synthetic organic compounds (SOCs; phenanthrene and biphenyl) by two pristine graphene nanosheets (GNS) and one graphene oxide (GO) was examined and compared with those of a coal base activated carbon (HD4000), a single-walled carbon nanotube (SWCNT), and a multi-walled carbon nanotube (MWCNT) in distilled and deionized water and in the presence of natural organic matter (NOM). Graphenes exhibited comparable or better adsorption capacities than carbon nanotubes (CNTs) and granular activated carbon (GAC) in the presence of NOM. The presence of NOM reduced the SOC uptake of all adsorbents. However, the impact of NOM on the SOC adsorption was smaller on graphenes than CNTs and activated carbons. Furthermore, the SOC with its flexible molecular structure was less impacted from NOM preloading than the SOC with planar and rigid molecular structure. The results indicated that graphenes can serve as alternative adsorbents for removing SOCs from water. However, they will also, if released to environment, adsorb organic contaminants influencing their fate and impact in the environment.

Ultrasonic pretreatment and subsequent anaerobic digestion under different operational conditions

In this study ultrasonic pretreatment was investigated in order to improve anaerobic digestion. First, the most effective sonication time was selected during the preliminary studies conducted on waste activated sludge samples. Then the optimal time selected was confirmed running batch anaerobic reactors. In the last part of the experiments, the effect of sonication was investigated for different operational conditions of semi-continuous digesters. Preliminary studies showed 15 min of sonication increased 50 mg/L initial soluble COD concentration up to a value of 2500 mg/L. Batch anaerobic digester results indicated that the increased soluble substrate improved anaerobic biodegradability concurrently, again with the maximal improvement observed for 15 min of sonication. Results from semi-continuous reactors indicated that at SRT of 15 days and OLR of 0.5 kg/m(3) d, ultrasonic pretreatment improved the daily biogas production, methane production and volatile solids reduction significantly when compared to control system. During the operation of reactors at 7.5 days of SRT, pretreatment helped to keep the reactors working. A simple economical analysis of the system was performed using the data obtained during the laboratory study.

Predictive model development for adsorption of aromatic contaminants by multi-walled carbon nanotubes.

In the present study, Quantitative Structure-Activity Relationship (QSAR) and Linear Solvation Energy Relationship (LSER) techniques were used to develop predictive models for adsorption of organic contaminants by multi-walled carbon nanotubes (MWCNTs). Adsorption data for 29 aromatic compounds from literature (i.e., the training data) including some of the experimental results obtained in our laboratory were used to develop predictive models with multiple linear regression analysis. The generated QSAR (r(2) = 0.88), and LSER (r(2) = 0.83) equations were validated externally using an independent validation data set of 30 aromatic compounds. External validation accuracies indicated the success of parameter selection, data fitting ability, and the prediction strength of the developed models. Finally, the combination of training and validation data were used to obtain a combined LSER equation (r(2) = 0.83) that would be used for predicting adsorption of a wide range of low molecular weight aromatics by MWCNTs. In addition, LSER models at different concentrations were generated, and LSER parameter coefficients were examined to gain insights to the predominant adsorption interactions of low molecular weight aromatics on MWCNTs. The molecular volume term (V) of the LSER model was the most influential descriptor controlling adsorption at all concentrations. At higher equilibrium concentrations, hydrogen bond donating (A) and hydrogen bond accepting (B) terms became significant in the models. The results demonstrate that successful predictive models can be developed for the adsorption of organic compounds by CNTs using QSAR and LSER techniques.

Impact of carbon nanotube morphology on phenanthrene adsorption

The present study examined the roles of the specific surface area (SSA), diameter, and length of carbon nanotubes (CNT) on the adsorption of phenanthrene (PNT) by analyzing the adsorption isotherms obtained with several single-walled carbon nanotubes (SWNT) and multiwalled carbon nanotubes (MWNT). At low equilibrium concentrations (e.g., 1 ppb), MWNTs with larger outer diameters exhibited higher PNT adsorption capacity on an SSA basis than those with smaller diameters. With increasing equilibrium concentration, adsorption on an SSA basis became independent of MWNT diameter, and the total surface area controlled maximum adsorption capacity. A similar analysis for the adsorption of naphthalene, a planar molecule with one less benzene ring but 20 times higher solubility than PNT, showed no correlation with respect to MWNT outer diameter. The results indicated that the surface curvature of MWNT was more important on the adsorption of PNT than on the adsorption of naphthalene. Specific surface area normalized isotherms did not show a correlation between PNT adsorption and lengths of SWNTs and MWNTs. Characterization results indicated that the morphology of CNTs plays an important role on the SSA and pore volume. Data from the manufacturer may not always represent the characteristics of CNTs in a particular batch. Therefore, accurate characterization of CNTs is critical to systematically examine the behavior of CNTs, such as adsorption and transport, in environmental systems.

Comparing graphene, carbon nanotubes, and superfine powdered activated carbon as adsorptive coating materials for microfiltration membranes

Multi-walled carbon nanotubes (MWCNTs), nano-graphene platelets (NGPs), and superfine powdered activated carbon (S-PAC) were comparatively evaluated for their applicability as adsorptive coatings on microfiltration membranes. The objective was to determine which materials were capable of contaminant removal while causing minimal flux reduction. Methylene blue and atrazine were the model contaminants. When applied as membrane coatings, MWCNTs had minimal retention capabilities for the model contaminants, and S-PAC had the fastest removal. The membrane coating approach was also compared with a stirred vessel configuration, in which the adsorbent was added to a stirred flask preceding the membrane cell. Direct application of the adsorbent to the membrane constituted a greater initial reduction in permeate concentrations of the model contaminants than with the stirred flask setup. All adsorbents except S-PAC showed flux reductions less than 5% after application as thin-layer membrane coatings, and flux recovery after membrane backwashing was greater than 90% for all materials and masses tested.

Adsorption of halogenated aliphatic contaminants by graphene nanomaterials.

In this study, adsorption of ten environmentally halogenated aliphatic synthetic organic compounds (SOCs) by a pristine graphene nanosheet (GNS) and a reduced graphene oxide (rGO) was examined, and their adsorption behaviors were compared with those of a single-walled carbon nanotube (SWCNT) and a granular activated carbon (GAC). In addition, the impacts of background water components (i.e., natural organic matter (NOM), ionic strength (IS) and pH) on the SOC adsorption behavior were investigated. The results indicated HD3000 and SWCNT with higher microporous volumes exhibited higher adsorption capacities for the selected aliphatic SOCs than graphenes, demonstrating microporosity of carbonaceous adsorbents played an important role in the adsorption. Analysis of adsorption isotherms demonstrated that hydrophobic interactions were the dominant contributor to the adsorption of aliphatic SOCs by graphenes. However, π-π electron donor-acceptor and van der Waals interactions are likely the additional mechanisms contributing to the adsorption of aliphatic SOCs on graphenes. Among the three background solution components examined, NOM showed the most influential effect on adsorption of the selected aliphatic SOCs, while pH and ionic strength had a negligible effects. The NOM competition on aliphatic adsorption was less pronounced on graphenes than SWCNT. Overall, in terms of adsorption capacities, graphenes tested in this study did not exhibit a major advantage over SWCNT and GAC for the adsorption of aliphatic SOCs.

Adsorption of organic contaminants by graphene nanosheets, carbon nanotubes and granular activated carbons under natural organic matter preloading conditions.

The effect of NOM preloading on the adsorption of phenanthrene (PNT) and trichloroethylene (TCE) by pristine graphene nanosheets (GNS) and graphene oxide nanosheet (GO) was investigated and compared with those of a single-walled carbon nanotube (SWCNT), a multi-walled carbon nanotube (MWCNT), and two coal based granular activated carbons (GACs). PNT uptake was higher than TCE by all adsorbents on both mass and surface area bases. This was attributed to the hydrophobicity of PNT. The adsorption capacities of PNT and TCE depend on the accessibility of the organic molecules to the inner regions of the adsorbent which was influenced from the molecular size of OCs. The adsorption capacities of all adsorbents decreased as a result of NOM preloading due to site competition and/or pore/interstice blockage. However, among all adsorbents, GO was generally effected least from the NOM preloading for PNT, whereas there was not observed any trend of NOM competition with a specific adsorbent for TCE. In addition, SWCNT was generally affected most from the NOM preloading for TCE and there was not any trend for PNT. The overall results indicated that the fate and transport of organic contaminants by GNSs and CNTs type of nanoadsorbents and GACs in different natural systems will be affected by water quality parameters, characteristics of adsorbent, and properties of adsorbate.

Influence of carbon nanotubes on the bioavailability of fluoranthene

Concurrent with the increase in the use of carbon nanotubes (CNTs) in society is the rise of their introduction into the environment. Carbon nanotubes cause adverse effects themselves, and they have the potential to adsorb contaminants such as polycyclic aromatic hydrocarbons (PAHs). Although CNTs have a high adsorption capacity for PAHs and these contaminants can co-occur in the environment, few studies have characterized the bioavailability of CNT-adsorbed PAHs to fish. The goal of the present study was to characterize the bioavailability of fluoranthene adsorbed to suspended multiwalled-carbon nanotubes (MWNTs) in freshwater containing natural organic matter (NOM). Adsorption isotherms indicated that NOM influenced the adsorption of fluoranthene to MWNTs, although in the absence of MWNTs it did not influence the bioavailability of fluoranthene to Pimephales promelas. Pimephales promelas were exposed for 16 h in synthetic moderately hard water containing fluoranthene in the presence of different concentrations of NOM, and fluoranthene adsorbed to MWNTs in the presence of NOM. Bioavailable fluoranthene was quantified in each exposure through bile analysis using fluorescence spectrophotometry. By comparing the concentration of fluoranthene metabolites in the bile with the concentration of fluoranthene added to MWNT and NOM solutions, the relative bioavailability of fluoranthene adsorbed to MWNTs was quantified. Results indicate that approximately 60% to 90% of the fluoranthene was adsorbed to the MWNTs and that adsorbed fluoranthene was not bioavailable to P. promelas. The results also suggest that fluoranthene is not desorbed from ingested MWNT, and the bioavailable fraction is only the freely dissolved fluoranthene in the aqueous phase.

Mechanisms and modeling of halogenated aliphatic contaminant adsorption by carbon nanotubes

This paper examines the adsorption of environmentally relevant halogenated aliphatic compounds using single-walled (SWCNT) and multi-walled carbon nanotubes (MWCNT), and the development of linear solvation-energy relationships (LSER) to examine those adsorption mechanisms. The poly-parameter LSER model was also compared to those previously generated for the adsorption of aromatic compounds by CNTs. The adsorption affinity of aliphatic compounds was greater on the SWCNT than MWCNT with similar oxygen contents. This was attributed to the pore-filling mechanism that was enhanced by higher micropore volume of the SWCNT bundles over the MWCNT bundles. LSER models showed that, at higher concentrations, B (the hydrogen bond accepting ability) was the most influential descriptor for both SWCNT and MWCNT. Other important descriptors were V followed by P, both of which exhibited a positive correlation with adsorption, indicating that their size and polarizability favors adsorption. The contribution of these descriptors to overall adsorption was 2-3 times less than the B. In comparison, V was the most important descriptor in the aromatic compound LSER models. This difference indicates that adsorbate hydrophobicity greatly affects the adsorption of aromatic compounds by CNTs, whereas, aliphatic compounds are affected by both the hydrophobic driving force and other interactions.

Adsorption of organic contaminants by graphene nanosheets: A review

Graphene nanosheets (GNS) such as graphenes and graphene oxides (GOs) have been widely investigated as next-generation adsorbents in both water and wastewater treatment processes due to their unique physicochemical properties and their affinity towards different classes of organic contaminants (OCs). In the last five years, more than 40 articles investigating adsorption of different classes of OCs by graphene and GO were published in peer-reviewed journals. Adsorption mechanisms were controlled by molecular properties of OCs (e.g., aromatic vs aliphatic, molecular size and hydrophobicity), characteristics of adsorbents (e.g., surface area, pore size distribution, and surface functional groups), and background solution properties (e.g., pH, ionic strength, surfactants, NOM, and temperature). This literature survey includes: (i) a summary of adsorption of OCs by GNS, (ii) a comprehensive discussion of the mechanisms and factors controlling the adsorption of OCs by GNS and a comparison of their adsorption behaviors with those of CNT. This literature survey also identifies future research needs and challenges on the adsorption of OCs by GNS.