Zhiguo Pei

Coadsorption of ciprofloxacin and Cu(II) on montmorillonite and kaolinite as affected by solution pH.

The coadsorption of ciprofloxacin (Cip) and Cu(II) on montmorillonite and kaolinite was studied between pH 4.0 and 9.5. At pH < 5.0, Cu(2+), Cip(+) and [Cu(II)(Cip(+/-))](2+) were the main species in solution. Between pH 5.0-7.0 [Cu(II)(Cip(+/-))](2+) was the dominant complex species. Above pH 8.0 [Cu(II)(Cip(-))(2)](0) precipitated. The presence of Cu(II) exerted no effect on the Cip sorption onto montmorillonite at low pH, whereas it increased Cip sorption on montmorillonite at pH > 6.0 due to the stronger affinity of Cip-Cu(II) complexes compared to sole Cip(-) or Cip(+/-), or Cip sorption via a Cu(II) bridge increased. In contrast, Cip increased Cu(II) adsorption on montmorillonite at pH < 7.0, whereas it decreased the adsorption of Cu(II) on kaolinite at pH 6.0-8.0. Cip was sorbed onto the kaolinite surface via interaction of carboxyl groups over the entire pH range. At pH 4.0-4.7, Cip(+) sorption onto kaolinites positively charged surface was more favorable than sorption of Cip-Cu(II) complexes. Batch experiments and FTIR analyses indicated that the coordination between Cip(+/-), Cip(-) and Cu(II) were most likely present on kaolinite surface at pH 7.0. At pH > 8.0, Cu(OH)(2) (s) and [Cu(II)(Cip(-))(2)](0) precipitated out of solution or on the montmorillonite or kaolinite surface, which was not considered evidence for either the sorption of Cip or the adsorption of Cu(II).

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.

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.

Citric Acid Enhanced Copper Removal by a Novel Multi-amines Decorated Resin

Cu removal by a novel multi-amines decorated resin (PAMD) from wastewater in the absence or presence of citric acid (CA) was examined. Adsorption capacity of Cu onto PAMD markedly increased by 186% to 5.07 mmol/g in the presence of CA, up to 7 times of that onto four commercial resins under the same conditions. Preloaded and kinetic studies demonstrated adsorption of [Cu-CA] complex instead of CA site-bridging and variations of adsorbate species were qualitatively illustrated. The interaction configuration was further studied with ESI-MS, FTIR, XPS and XANES characterizations. The large enhancement of Cu adsorption in Cu-CA bi-solutes systems was attributed to mechanism change from single-site to dual-sites interaction in which cationic or neutral Cu species (Cu2+ and CuHL0) coordinated with neutral amine sites and anionic complex species (CuL− and Cu2L22−) directly interacted with protonated amine sites via electrostatic attraction, and the ratio of the two interactions was approximately 0.5 for the equimolar bi-solutes system. Moreover, commonly coexisting ions in wastewaters had no obvious effect on the superior performance of PAMD. Also, Cu and CA could be recovered completely with HCl. Therefore, PAMD has a great potential to efficiently remove heavy metal ions from wastewaters in the presence of organic acids.

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.

Sorption of aromatic hydrocarbons onto montmorillonite as affected by norfloxacin

Effect of norfloxacin (Nor) on the sorption of 1,3-dinitrobenzene (1,3-DNB), and PAHs (naphthalene (NAPH), phenanthrene (PHEN) and pyrene (PYR)) to K(+)-montmorillonite was studied. Nor suppressed 1,3-DNB sorption due to their competition for the same sorption sites. 1,3-DNB was sorbed on K(+)-montmorillonite surface via cation-polar interaction and n-π electron donor-acceptor interaction. Nor also was sorbed on these sites through cation exchange, cation bridging and/or surface complexation. Nor increased three PAHs sorption on montmorillonite and the enhanced magnitude was positively correlated with the π-donor strength of three PAHs. The enhanced sorption of PAHs by Nor was primarily attributed to π-π interaction between π-electron-depleted quinoline ring of Nor and π-electron-rich PAHs. Compared with cation (Nor(+)) and anion (Nor(-)), zwitterion (Nor(±)) of Nor increased PHEN and PYR sorption more pronounced due to additional cation-π interaction between the sorbed Nor(±) and PAHs. (1)H NMR spectrum provided direct evidence for π-π and cation-π complexation between PAHs and Nor(+) in solution by ring-current-induced upfield chemical shifts of amino group and methylene group of Nor(+).

Adsorption and desorption of 2,4,6-trichlorophenol onto and from ash as affected by Ag+, Zn2+, and Al3+

Metal cations and organic pollutants mostly co-exist in the natural environment. However, their interactions in adsorption processes have yet to be adequately addressed. In the current study, the effect of inorganic cations with different charges (Ag+, Zn2+, and Al3+) on the adsorption and desorption of 2,4,6-trichlorophenol (TCP) onto and from processed ash derived from wheat (Triticum aestivum L.) straw was investigated. The adsorption and desorption of TCP were both nonlinear; the isotherm and kinetics curves fitted well using the Freundlich equation and a pseudo-second-order model, respectively. The presence of Ag+ promoted TCP adsorption, while Zn2+ and Al3+ reduced TCP adsorption onto ash. The desorption of TCP from ash showed obvious hysteresis, and the presence of Ag+, Zn2+, and Al3+ caused the desorption to be less hysteretic. The suppression of TCP adsorption by Zn2+ and Al3+ was ascribed to the partial overlapping of adsorption groups between TCP and metal ions. Al3+ had a stronger inhibition effect than that of Zn2+ due to its higher binding capacity and larger hydrated ionic radius than those of Zn2+. Enhanced adsorption of TCP onto ash by Ag+ was ascribed to its ability to reduce the competitive adsorption of water molecules on ash surface by replacing the original ions, such as Na+ and Ca2+, and compressing the hydrated ionic radius of these metal ions. In addition, Ag+ was able to bind with the aromatic organic compounds containing π-electrons, which resulted in a further increase of TCP adsorption by ash.