Ya-Ning Xie

Adsorption of 2,4,6-trichlorophenol by multi-walled carbon nanotubes as affected by Cu(II)

Adsorption equilibrium of 2,4,6-trichlorophenol (TCP) on multi-walled carbon nanotubes (MWCNTs) was investigated to explore the possibility of using MWCNTs for concentration, detection and removal of TCP from contaminated water. The adsorption of TCP on MWCNTs at pH 4 was nonlinear, reversible and best fit by a Polanyi-Manes model. Oxidation treatment increased surface area and introduced hydrophilic carboxylic groups to the defect sites of MWCNTs, hence increased the sorption of TCP and Cu(II) individually. Cu(II) suppressed the sorption of TCP on oxidized MWCNTs15A, but had little effect on as-grown MWCNTs15. TCP had no influence on Cu(II) sorption to either. The mechanisms of Cu(II) suppression effect on TCP adsorption are ascribed to the formation of surface complexes of Cu(II), which was verified by X-ray absorption spectroscopy. Cu(II) exerts a cross-linking effect of functional groups on adjacent tubes, creating a more tightly knit bundle and suppressing the condensation of TCP in the pore spaces between the tubes. The large hydration sphere around surface complexes of Cu(II) may also intrude or shield hydrophilic sites, leading to the crowding out of TCP around the Cu(II)-complexed sites.

Adsorption of diuron and dichlobenil on multiwalled carbon nanotubes as affected by lead.

The effect of lead on the adsorption of diuron and dichlobenil on multiwalled carbon nanotubes (MWCNTs) was investigated to explore the possible application of MWCNTs for removal of both herbicides from contaminated water. The adsorption of diuron and dichlobenil on MWCNTs at pH 6 was nonlinear and fit the Polanyi-Manes model well. The adsorption of diuron and dichlobenil was closely correlated with specific surface areas and micropore volumes of MWCNTs. An increase in oxygen content of MWCNTs with same diameters and similar surface areas decreased the adsorption of diuron and dichlobenil, while increased the adsorption of lead. Micro-Fourier transform infrared spectroscopic study indicated that hydrogen bonding is a main mechanism responsible for the adsorption of diuron or dichlobenil onto MWCNTs-O. Oxygen containing groups, mainly carboxylic groups, significantly increased the adsorption of lead through the formations of outer-sphere and inner-sphere complexes, which are verified by X-ray absorption spectroscopic measurements. Oxygen containing groups and the presence of lead diminished the adsorption of diuron and dichlobenil. The suppression mechanisms of lead were ascribed to hydration and complexation of lead with carboxylic groups, which may occupy part of surface of MWCNTs-O. The large hydration shell of lead cations may intrude or shield hydrophobic and hydrophilic sites, resulting in a decreased adsorption of diuron and dichlobenil at the lead-complexed moieties.

Characterization of Pb, Cu, and Cd adsorption on particulate organic matter in soil

Evidence exists for significant metal enrichment in particulate organic matter (POM) compared to other soil constituents, but the relevant mechanisms are poorly understood. In the present study, adsorption of the heavy metals Pb, Cu, and Cd on a loamy soil and on POM separated from this soil was investigated. The adsorption kinetic data can be well described with a pseudo-second order model, whereas the equilibrium data are well fitted by a Langmuir model. Adsorption isotherms and kinetics data, in addition to the influence of pH on metal adsorption, showed that POM had a much higher adsorption capacity for Pb, Cu, and Cd compared to the whole soil. Ionic strength effects on metal adsorption, Fourier transform infrared spectroscopy, x-ray absorption spectroscopy x-ray absorption spectroscopy including x-ray absorption near-edge structure and extended x-ray absorption fine-structure spectroscopy were employed to elucidate the adsorption mechanisms. The results suggested that Pb and Cu adsorption on POM was mainly through inner-sphere complexes with carboxyl and hydroxyl groups. Cadmium was possibly adsorbed via outer-sphere complexation, indicated by the influence of ionic strength on Cd adsorption.

Organic acids enhance the uptake of lead by wheat roots

The uptake and bioavailability of lead (Pb) in soil–plant systems remain poorly understood. This study indicates that acetic and malic acids enhance the uptake of Pb by wheat (Triticum aestivum L.) roots under hydroponic conditions. The net concentration-dependent uptake influx of Pb in the presence and absence of organic acids was characterized by Michaelis–Menten type nonsaturating kinetic curves that could be resolved into linear and saturable components. Fitted maximum uptake rates (Vmax) of the Michaelis–Menton saturable component in the presence of acetic and malic acids were, respectively, 2.45 and 1.63 times those of the control, while the Michaelis–Menten Km values of 5.5, 3.7 and 2.2xa0μM, respectively, remained unchanged. Enhanced Pb uptake by organic acids was partially mediated by Ca2+ and K+ channels, and also depended upon the physiological function of the plasma membrane P-type ATPase. Uptake may have been further enhanced by an effectively thinner unstirred layer of Pb adjacent to the roots, leading to more rapid diffusion towards roots. X-ray absorption spectroscopic studies provided evidence that the coordination environment of Pb in wheat roots was similar to that of Pb(CH3COO)2·3H2O in that one Pb atom was coordinated to four oxygen atoms via the carboxylate group.

Insight to ternary complexes of co-adsorption of norfloxacin and Cu(II) onto montmorillonite at different pH using EXAFS.

Co-adsorption of norfloxacin (Nor) and Cu(II) on montmorillonite at pH 4.5, 7.0 and 9.0 was studied by integrated batch adsorption experiments and extended X-ray absorption fine structure (EXAFS) spectroscopy. Under such pH conditions the dominant species of Nor are cation (Nor(+)), zwitterion (Nor(±)), and anion (Nor(-)), respectively. Results indicated that Nor sorption decreased with an increase of solution pH. The presence of Cu(II) slightly suppressed the Nor(+) sorption at pH 4.5, while increased Nor(±) and Nor(-)sorption on montmorillonite at pH 7.0 and 9.0, respectively. In contrast, Nor increased Cu(II) adsorption at pH 4.5, but had little effect on the adsorption of Cu(II) on montmorillonite at pH 7.0 and 9.0. Spectroscopic results showed that, at pH 4.5, Nor(+) was sorbed on montmorillonite by the formation of outer-sphere montmorillonite-Nor-Cu(II) ternary surface complex. At pH 7.0, montmorillonite-Nor-Cu(II) and montmorillonite-Cu(II)-Nor ternary surface complexes co-exist. At pH 9.0, montmorillonite-Cu(II)-Nor ternary surface complex was likely formed, which was different to Cu(II)(Nor)(2) precipitate of the solution.

Effects of metal cations on sorption-desorption of p-nitrophenol onto wheat ash.

The mutual effects of metal cations (Cu2+, Pb2+, Zn2+, and Cd2+) and p-nitrophenol (NP) on their adsorption desorption behavior onto wheat ash were studied. Results suggested that Cu2+, Pb2+, and Zn2+ diminished the adsorption and increased the desorption of NP remarkably, while Cd2+ had no such effect. In contrast, NP diminished the adsorption of Cu2+, Pb2+, and Zn2+ onto ash, however, this suppression effect depended on the initial concentrations of metal cations. NP had no effect on Cd2+ adsorption on ash. Fourier transform infrared (FT-IR) and X-ray absorption spectroscopic (XAS) studies suggested the following mechanisms responsible for the metal suppression effect on NP adsorption: (1) large hydrated Cu2+, Pb2+, and Zn2+ shells occupied the surface of ash and prevent nonspecific adsorption of NP onto ash surface; (2) Cu2+, Pb2+, and Zn2+ may block the micropores of ash, resulting in decreased adsorption of NP; (3) complexation of Cu2+, Pb2+, and Zn2+ was likely via carboxyl, hydroxylic and phenolic groups of wheat ash and these same groups may also react with NP during adsorption. As a soft acid, Cd2+ is less efficient in the complexation of oxygen-containing acid groups than Cu2+, Pb2+, and Zn2+. Thus, Cd2+ had no effect on the adsorption of NP on wheat ash.

Arsenate sorption on two chinese red soils evaluated with macroscopic measurements and extended X‐ray absorption fine‐structure spectroscopy

Arsenic sorption is the primary factor that affects the bioavailability and mobility of arsenic in soils. To elucidate the characteristics and mechanisms of arsenate, As(V), sorption on soils, a combination of sorption isotherms, zeta potential measurements, and extended X-ray absorption fine-structure (EXAFS) spectroscopy was used to investigate As(V) sorption on two Chinese red soils. Arsenate sorption increased with increasing As(V) concentration and was insensitive to ionic strength changes at pH 6.0. Arsenate, mainly as H2AsO4- in soil solution at pH 6.0, was strongly sorbed mainly through ligand exchange by the two soils. The sorption capacity was affected by the iron and aluminum mineral contents in the soils. The zeta potential measurements showed that As(V) sorption lowered the zeta potential and the points of zero charge of the soils. The EXAFS data indicate that adsorbed As(V) forms inner-sphere complexes with bidentate-binuclear configurations, as evidenced by an As-Fe bond distance of 3.28 +/- 0.04 A and an As-Al bond distance of 3.17 +/- 0.03 A. The two As(V) complexes were stable at different As(V) loadings, whereas the proportions were related to the aluminum and iron mineral contents in the soils. This study illuminated the importance of inclusion of microscopic and macroscopic experiments to elucidate sorption behavior and mechanisms.

Sorption of p-nitrophenol on two Chinese soils as affected by copper

Heavy metals and organic contaminants often coexist in soils. However, very little information is available regarding the effect of metals on the sorption of organic contaminants onto soils and/or of organic contaminants on metal sorption. In the present study, the effect of Cu on the sorption of p-nitrophenol on two Chinese soils was investigated using a batch-equilibration method for three conditions: Copper and p-nitrophenol were sorbed simultaneously, either Cu orp-nitrophenol was sorbed previously, or the soil colloidal phase was removed in part previously. The results suggested that Cu suppressed the sorption ofp-nitrophenol on soils, whereas p-nitrophenol had little effect on Cu sorption because of the higher affinity of Cu for soils. Mechanisms of the Cu suppression effect were suggested by the results. First, large hydrated Cu occupy the siloxane surface of soils and prevent nonspecific interaction between p-nitrophenol and soils. Second, the soil colloidal phase is an effective adsorbent of p-nitrophenol; thus, more p-nitrophenol is retained in the aqueous phase. In addition, the aggregation of the colloidal particles may occur, which blocks soil pores, thereby decreasing the sorption of p-nitrophenol on the solid soil phase. Third, x-ray absorption spectroscopy revealed that Cu forms inner-sphere complexes with the carboxyl and hydroxyl functional moieties of the soil particles (clay minerals and organic matter). Fourier-transform infrared spectroscopy study indicated that these groups also react with p-nitrophenol through H-bond formation. These results suggested that Cu and p-nitrophenol have common sorption sites, at least in the soil organic matter domain, which is partially responsible for the observed overall Cu suppression effect.

Impact of pyrolysis process on the chromium behavior of COPR.

The effect of pyrolysis process with sewage sludge on the chromium behavior of chromite ore processing residue (COPR) was examined in this study. The behavior of chromium was characterized in term of chromium oxidation test, pH-static leaching tests, column leaching test and sequential extraction test. As a sequence of pyrolysis process, the Cr(VI) in COPR was effectively reduced from 5057 mg kg(-1) for untreated COPR to 8.6 mg kg(-1) for treated COPR at temperature over 600 degrees C, which is far below the New Jersey Department of Environmental Protection regulatory limit of 240 mg kg(-1). As a result, the amount of exchangeable and carbonate-bound Cr fractions, the most mobile for the environment, were largely reduced. At the same time, the amount of the other three Cr fractions which are much less mobile become augmented. pH static test showed that the chromium in the treated COPR at pyrolysis temperature above 400 degrees C was quite stable at pH>7. Column study also indicated that only negligible amount of chromium of the treated COPR at above 600 degrees C can be released by the acid rain.