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Adsorption and desorption of arsenate on sandy sediments from contaminated and uncontaminated saturated zones: Kinetic and equilibrium modeling
2016
Hafeznezami, Saeedreza | Zimmer-Faust, Amity G. | Dunne, Aislinn | Tran, Tiffany | Yang, Chao | Lam, Jacquelyn R. | Reynolds, Matthew D. | Davis, James A. | Jay, Jennifer A.
Application of empirical models to adsorption of contaminants on natural heterogeneous sorbents is often challenging due to the uncertainty associated with fitting experimental data and determining adjustable parameters. Sediment samples from contaminated and uncontaminated portions of a study site in Maine, USA were collected and investigated for adsorption of arsenate [As(V)]. Two kinetic models were used to describe the results of single solute batch adsorption experiments. Piecewise linear regression of data linearized to fit pseudo-first order kinetic model resulted in two distinct rates and a cutoff time point of 14–19 h delineating the biphasic behavior of solute adsorption. During the initial rapid adsorption stage, an average of 60–80% of the total adsorption took place. Pseudo-second order kinetic models provided the best fit to the experimental data (R2 > 0.99) and were capable of describing the adsorption over the entire range of experiments. Both Langmuir and Freundlich isotherms provided reasonable fits to the adsorption data at equilibrium. Langmuir-derived maximum adsorption capacity (St) of the studied sediments ranged between 29 and 97 mg/kg increasing from contaminated to uncontaminated sites. Solid phase As content of the sediments ranged from 3.8 to 10 mg/kg and the As/Fe ratios were highest in the amorphous phase. High-pH desorption experiments resulted in a greater percentage of solid phase As released into solution from experimentally-loaded sediments than from the unaltered samples suggesting that As(V) adsorption takes place on different reversible and irreversible surface sites.
Show more [+] Less [-]Selenite sorption by carbonate substituted apatite
2016
Moore, Robert C. | Rigali, Mark J. | Brady, Patrick
The sorption of selenite, SeO32−, by carbonate substituted hydroxylapatite was investigated using batch kinetic and equilibrium experiments. The carbonate substituted hydroxylapatite was prepared by a precipitation method and characterized by SEM, XRD, FT-IR, TGA, BET and solubility measurements. The material is poorly crystalline, contains approximately 9.4% carbonate by weight and has a surface area of 210.2 m2/g. Uptake of selenite by the carbonated hydroxylapatite was approximately an order of magnitude higher than the uptake by uncarbonated hydroxylapatite reported in the literature. Distribution coefficients, Kd, determined for the carbonated apatite in this work ranged from approximately 4200 to over 14,000 L/kg. A comparison of the results from kinetic experiments performed in this work and literature kinetic data indicates the carbonated apatite synthesized in this study sorbed selenite 23 times faster than uncarbonated hydroxylapatite based on values normalized to the surface area of each material. The results indicate carbonated apatite is a potential candidate for use as a sorbent for pump-and-treat technologies, soil amendments or for use in permeable reactive barriers for the remediation of selenium contaminated sediments and groundwaters.
Show more [+] Less [-]The effect of Cu2+ chelation on the direct photolysis of oxytetracycline: A study assisted by spectroscopy analysis and DFT calculation
2016
Jin, Xin | Qiu, Shanshan | Wu, Ke | Jia, Mingyun | Wang, Fang | Gu, Chenggang | Zhang, Aiqian | Jiang, Xin
The extensive usage of OTC and Cu2+ in livestock and poultry industry caused high residues in natural environment. Co-contamination of OTC and Cu2+ was a considerable environmental problem in surface waters. In this study, Cu2+ mediated direct photolysis of OTC was studied. Cu2+ chelating with OTC was found to greatly inhibit OTC photodegradation. To reveal the chelation mechanism of OTC-Cu complexes, multiple methods including UV–Vis absorption spectra, Infrared (IR) spectra, mass spectroscopy, and density functional theoretical (DFT) modeling were performed. Four OTC-Cu complexes were proposed. Cu2+ preferably bond to O11O12 site with the binding constants logK = 8.19 and 7.86 for CuHL+ and CuL±, respectively. The second chelating site was suggested to be O2O3 with the binding constants of logK = 4.41 and 4.62 for Cu2HL3+ and Cu2L2+, respectively. The suppressed quantum yield of OTC by Cu2+ chelation was accused for their intra-/inter-molecular electron transfer, by which the energy in activated states was distributed. The occurrence of electron transfer between BCD ring and A ring also from BCD ring to Cu was evidenced by the TD-DFT result only for the OTC-Cu complexes. Besides, the cyclic voltammetry measurement also suggested one OTC-Cu(II)/OTC-Cu(I) redox couple. These results suggested that the persistence of OTC in environmental surface waters will probably be underestimated for neglecting the chelating effect of Cu2+. The photolysis quantum yield of OTC-Cu complexes, as well as the specific molar absorption constants, the equilibrium binding constants of Cu2+ with OTC could contribute to more accurate kinetic models of OTC.
Show more [+] Less [-]Does cadmium affect the toxicokinetics of permethrin in Chironomus dilutus at sublethal level? Evidence of enzymatic activity and gene expression
2016
Chen, Xin | Li, Huizhen | Zhang, Junjie | Ding, Yuping | Yau, Ching
Pyrethroids and metals were simultaneously detected in aquatic environment and showed antagonistic lethality to the benthic invertebrate, Chironomus dilutus. Accelerated biotransformation of pyrethroids in organism by the presence of metals was proposed as the likely reason for the antagonism. Mechanistic explanation for the role of toxicokinetics of pyrethroids in the antagonistic interaction would help better understanding the reasons for the joint toxicity. The goal was achieved in the current study by evaluating the impact of cadmium on toxicokinetic parameters of permethrin in C. dilutus, and by explaining the interaction through quantifying the activity and gene expression of biotransformation-related enzymes. Toxicokinetic parameters were simulated using a first-order kinetic model. Bioconcentration factors and uptake and elimination rate constants for permethrin were not significantly changed with the addition of cadmium at sublethal level, neither did the activity of enzymes, including glutathione S-transferase (GST), carboxylesterase (CarE), catalase and lipid peroxidation. Yet, the activities of metabolism-related enzymes (GST and CarE) showed an elevating tendency with adding cadmium. Furthermore, the expression of metabolism-related genes, including cytochrome P450 and glutathione S-transferase genes were significantly up-regulated in C. dilutus exposed to a mixture of permethrin and cadmium compared with permethrin only. Although co-exposure to cadmium did not induce toxicokinetic changes of permethrin in C. dilutus, it did enhance the activity of metabolic enzymes which were encoded by the metabolism-related genes, suggesting an acceleration of biotransformation of permethrin to less toxic metabolites in the midges. This possibly explained the antagonistic interaction for permethrin and cadmium.
Show more [+] Less [-]Sequential biodegradation of complex naphtha hydrocarbons under methanogenic conditions in two different oil sands tailings
2016
Mohamad Shahimin, Mohd Faidz | Siddique, Tariq
Methane emissions in oil sands tailings ponds are sustained by anaerobic biodegradation of unrecovered hydrocarbons. Naphtha (primarily C6–C10; n- iso- and cycloalkanes) is commonly used as a solvent during bitumen extraction process and its residue escapes to tailings ponds during tailings deposition. To investigate biodegradability of hydrocarbons in naphtha, mature fine tailings (MFT) collected from Albian and CNRL tailings ponds were amended with CNRL naphtha at ∼0.2 wt% (∼2000 mg L−1) and incubated under methanogenic conditions for ∼1600 d. Microbial communities in both MFTs started metabolizing naphtha after a lag phase of ∼100 d. Complete biodegradation/biotransformation of all n-alkanes (except partial biodegradation of n-octane in CNRL MFT) followed by major iso-alkanes (2-methylpentane, 3-methylhexane, 2- and 4-methylheptane, iso-nonanes and 2-methylnonane) and a few cycloalkanes (derivatives of cyclopentane and cyclohexane) was observed during the incubation. 16S rRNA gene pyrosequencing showed dominance of Peptococcaceae and Anaerolineaceae in Albian MFT and Anaerolineaceae and Syntrophaceae in CNRL MFT bacterial communities with co-domination of Methanosaetaceae and “Candidatus Methanoregula” in archaeal populations during active biodegradation of hydrocarbons. The findings extend the known range of hydrocarbons susceptible to methanogenic biodegradation in petroleum-impacted anaerobic environments and help refine existing kinetic model to predict greenhouse gas emissions from tailings ponds.
Show more [+] Less [-]Insight into the adsorption of PPCPs by porous adsorbents: Effect of the properties of adsorbents and adsorbates
2016
Zhu, Zengyin | Xie, Jiawen | Zhang, Mancheng | Zhou, Qing | Liu, Fuqiang
Adsorption is an efficient method for removal of pharmaceuticals and personal care products (PPCPs). Magnetic resins are efficient adsorbents for water treatment and exhibit potential for PPCP removal. In this study, the magnetic hypercrosslinked resin Q100 was used for adsorption of PPCPs. The adsorption behavior of this resin was compared with those of two activated carbons, namely, Norit and F400D. Norit exhibited the fastest adsorption kinetics, followed by Q100. Norit featured a honeycomb shape and long-range ordered pore channels, which facilitated the diffusion of PPCPs. Moreover, the large average pore size of Q100 reduced diffusion resistance. The adsorbed amounts of 11 PPCPs on the three adsorbents increased with increasing adsorbate hydrophobicity. For Q100, a significant linear correlation was observed between the adsorption performance for PPCPs and hydrophobicity (logD value) of adsorbates (R2 = 0.8951); as such, PPCPs with high logD values (>1.69) could be efficiently removed. Compared with those of Norit and F400D, the adsorption performance of Q100 was less affected by humic acid because of the dominant hydrophobic interaction. Furthermore, Q100 showed improved regeneration performance, which renders it promising for PPCP removal in practical applications.
Show more [+] Less [-]Adsorption-uptake-metabolism kinetic model on the removal of BDE-47 by a Chlorella isolate
2016
Deng, Dan | Tam, Nora F.Y.
Polybrominated diphenyl ethers (PBDEs) are persistent and toxic organic pollutants, causing hazardous to ecosystems and human health but are difficult to remove from contaminated environments. The mechanism and kinetics of a Chlorella isolate to remove BDE-47 were investigated. This species isolated from the influent of wastewater treatment plants in Hong Kong was PBDE tolerant. More than 80% of BDE-47 was removed in short- and long-term experiments lasting 1 h and 7 days, respectively. The dominant removal process was adsorption on cell surfaces, with 73% of the spiked BDE-47 removed within five minutes of exposure. As the exposure prolonged, the adsorption became saturated. BDE-47 on cell surfaces was then gradually taken up into cells. At the end of the 7-day exposure, 17% of the spiked BDE-47 was within cells, while 27% was metabolized. Four metabolites, including BDE-28, 6-OH- and 5-OH-BDE-47, and 6-MeO-BDE-47, were produced from the debromination, hydroxylation and methoxylation of BDE-47. The removal kinetics of BDE-47 by freshwater microalgae could be explained by the multi-compartmental adsorption-uptake-metabolism model developed in this study.
Show more [+] Less [-]Adsorption and desorption of dissolved organic matter by carbon nanotubes: Effects of solution chemistry
2016
Engel, Maya | Chefetz, Benny
Increasing use of carbon nanotubes (CNTs) has led to their introduction into the environment where they can interact with dissolved organic matter (DOM). This study focuses on solution chemistry effects on DOM adsorption/desorption processes by single-walled CNTs (SWCNTs). Our data show that DOM adsorption is controlled by the attachment of DOM molecules to the SWCNTs, and that the initial adsorption rate is dependent on solution parameters. Adsorbed amount of DOM at high ionic strength was limited, possibly due to alterations in SWCNT bundling. Desorption of DOM performed at low pH resulted in additional DOM adsorption, whereas at high pH, adsorbed DOM amount decreased. The extent of desorption conducted at increased ionic strength was dependent on pre-adsorbed DOM concentration: low DOM loading stimulated additional adsorption of DOM, whereas high DOM loading facilitated release of adsorbed DOM. Elevated ionic strength and increased adsorbed amount of DOM reduced the oxidation temperature of the SWCNTs, suggesting that changes in the assembly of the SWCNTs had occurred. Moreover, DOM-coated SWCNTs at increased ionic strength provided fewer sites for atrazine adsorption. This study enhances our understanding of DOM–SWCNT interactions in aqueous systems influenced by rapid changes in salinity, and facilitates potential use of SWCNTs in water-purification technologies.
Show more [+] Less [-]Preparation of PCL/Clay and PVA/Clay Electrospun Fibers for Cadmium (Cd+2), Chromium (Cr+3), Copper (Cu+2) and Lead (Pb+2) Removal from Water
2016
Fibrous mats of polymer/clay were obtained by electrospinning method, and their capacity for heavy metals removal from water was evaluated. Four different fibrous mats were prepared from a corresponding polymer/clay solutions. The precursor materials employed were poly-ε-caprolactone, polyvinyl alcohol polymers, kaolin, and metakaolin clays. Raw materials and the prepared fiber mats characterization were carried out using scanning electron microscopy, Fourier transformed infrared spectroscopy, X-ray diffraction, termogravimetric analysis, differential thermal analysis, and differential scanning calorimetry. Elemental composition of the materials was obtained using energy-dispersive X-ray spectroscopy. The environmental applications of polymer/clay materials were tested for water treatment by heavy metals (cadmium (Cd⁺²), chromium (Cr⁺³), copper (Cu⁺²), and lead (Pb⁺²)) sorption. Kinetic adsorption studies were conducted employing heavy metal solutions with initial concentration of 200 mg/L, and the amount of heavy metal adsorbed and kinetics parameters was determined using inductively coupled plasma-optical emission spectroscopy (ICP-OES). According to the kinetic data, the adsorption process of Cd⁺², Cr⁺³, Cu⁺², and Pb⁺² onto polymer/clay is favorable for the prepared materials and they follow a pseudo-first-order model according to the kinetic analysis. Additionally, the intraparticle diffusion was evaluated by applying the Morris and Weber model; in order to investigate the contribution of film resistance to the kinetics of the heavy metals adsorption, the adsorption kinetic data was further analyzed by Boyd’s film-diffusion model.
Show more [+] Less [-]Lime-Amended Semi-arid Soils in Retaining Copper, Lead, and Zinc from Aqueous Solutions
2016
Moghal, Arif Ali Baig | Reddy, Krishna R. | Mohammed, Syed Abu Sayeed | Al-Shamrani, Mosleh Ali | Zahid, Waleed M.
Most of the chemicals containing non-biodegradable metal pollutants from anthropogenic sources are highly mobile in nature. The only way to contain or limit their movement is through sorption and entrapment in the soil matrices. In this study, the sorptive response of the three most commonly found divalent metal contaminants, copper (Cu⁺²), lead (Pb⁺²), and zinc (Zn⁺²), are studied using two locally available semi-arid soils from Saudi Arabia. To enhance their retention capacity, these soils are amended with lime. The response to sorption at varying initial contaminant concentrations, pH conditions, temperature levels, and dilution ratios are investigated. Relying on empirical models (Langmuir and Freundlich), the nature of sorption (monolayer or heterogeneous) is ascertained. Further, kinetic models are employed to validate the type and nature of sorption that occurs (whether pseudo first-order or second-order). It is found that the experimental results correlate well with these empirical models for both the Al-Ghat and Al-Qatif soils when amended with lime and attenuate Cu, Pb, and Zn to satisfactory levels. The R ² values are close to 1 for all the tested models. The order of sorption was Pb > Cu > Zn for these heavy metals, and also for soils and soil mixtures that were considered: Al-Qatif soil amended with 6 % lime > Al-Ghat soil with 6 % lime > Al-Qatif > Al-Ghat. Lime-treated soils sorbed 73, 65, and 60 % more than the untreated soils for Pb, Cu, and Zn, respectively.
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