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To evaluate the synergetic adsorption capacity of layered double hydroxide (LDH) and photocatalytic reduction property of TiO2 for aqueous Cr(VI), the Fe3O4-ZnAl-LDH and TiO2 composites (FLT) were prepared via sol-gel method. The removal efficiency of FLT composites for Cr(VI) changed with the mass ratio of Fe3O4-LDH/TiO2, and the optimal ratio was 20% (FLT-2). The adsorption efficiencies of 100 mg FLT-2 were 74% and 64% for 20 and 50 mg/L Cr(VI) solution, and the total removal ratios of Cr(VI) were all over 97% after UV irradiation. The experimental data of adsorption kinetic, adsorption isothermal, and photocatalytic reduction were consistent with the pseudo-second-order, Langmuir, and first-order reaction equations, respectively. From the X–ray photoelectron spectra analysis, FLT composites adsorbed Cr(VI) directly via surface complexation, also reduced aqueous Cr(VI) to Cr(III). The photocurrent and electrochemical impedance spectroscopy of FLT composites indicated the photo-induced electron-hole pairs were separated effectively. The regeneration results show that the FLT composites had good stability and reusability after five consecutive cycles. Therefore, FLT composites are promising materials in the disposal of wastewater containing Cr(VI).

Reduced graphene oxide (rGO) is one of the most widely used carbon nanomaterials. When it is released into the environment, rGO can markedly affect the transformation of many pollutants, and change their fate and risk. In this work, the synergetic effects of rGO and Cu(II) on the oxidation of 2-naphthol were examined in water in the dark. It was found that the coexistence of rGO and Cu(II) significantly promoted the oxidation of 2-naphthol. Corresponding products were identified as the coupling oligomers of 2-naphthol (dimer, trimer and tetramer) and hydroxylated compounds (OH-2-naphthol, OH-dimer, di–OH–dimer and naphthoquinone derivatives). In the oxidation reaction, rGO played dual roles, i.e. adsorbent and electron-transfer mediator. rGO firstly adsorbed Cu(II) and 2-naphthol on its surface, and then transferred electrons from 2-naphthol to Cu(II) to yield 2-naphthol radicals and Cu(I). 2-Naphthol radicals coupled to each other to form different oligomers of 2-naphthol. Cu(I) was re-oxidized back to Cu(II) by dissolved oxygen, which sustained the continuous oxidation of 2-naphthol. During the autoxidation of Cu(I), reactive oxygen species were generated, which further reacted with 2-naphthol to form hydroxylated products. These findings provide new insights into the risk assessment of rGO and 2-naphthol in aquatic environments.

In this work, the magnetic alginate microsphere of Fe3O4/MgAl-LDH (Fe3O4/LDH-AM) was prepared by immobilizing the Fe3O4/LDH with calcium alginate (CA) and was used to remove Cd2+, Pb2+, and Cu2+ from aqueous solutions. The obtained Fe3O4/LDH-AM was characterized by X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, X-ray photoelectron spectroscopy, and Brunauer-Emmett-Teller surface area determination. The results indicated that the surface groups of the alginate and LDH were retained and so was the crystal structure in the alginate microsphere. The adsorption performance of the Fe3O4/LDH-AM for Cd2+, Pb2+, and Cu2+ in aqueous solutions was evaluated by batch and column adsorption experiments. The effects of adsorption conditions, kinetics, isotherms, mechanisms, and potential applications were investigated. The adsorption kinetic data conformed to the pseudo-second-order kinetic equation, and the isotherm data fit well with the Freundlich and Langmuir isotherm models. The adsorption mechanism of Cd2+, Pb2+, and Cu2+ by the Fe3O4/LDH-AM entailed complexation and precipitation. The experimental breakthrough curves were correlated with the Thomas model. Moreover, the Fe3O4/LDH-AM displayed superior regeneration and reusability. These results suggest that the Fe3O4/LDH-AM is an efficient adsorbent for the removal of heavy metals and can be effectively employed in practical applications.

Ionic antibiotics and metals generally coexist, and their interaction can affect their sorption behaviors onto soil minerals, therefore determining their environmental hazards. This study investigated the sorption and cosorption of Zn(II) and chlortetracycline (CTC) onto montmorillonite at different solution pH (3−10) using batch experiments and extended X-ray absorption fine structure (EXAFS) analysis. The Langmuir model could reproduce well the sorption isotherms of Zn(II) and CTC. The presence of CTC/Zn(II) could promote the maximum sorption capacity (Qm) of Zn(II)/CTC, based on site energy distribution (SED) theory. Generally, Zn(II) sorption increased with pH increasing. Comparatively, CTC sorption decreased as pH increased till approximately pH 5.0, then increased continuously with pH increasing. Both CTC and Zn(II) co-existence enhanced their individual sorption in both acidic and neutral environments. The processes behind CTC and Zn(II) sorption mainly included cation exchange and surface complexation. The EXAFS data evidenced that the presence of CTC could alter the species of Zn(II) on montmorillonite via surface complexation at pH 4.5 and 7.5, with Zn-CTC complexes being the predominant species on montmorillonite at pH 7.5. At pH 9.5, Zn(II) may exist onto montmorillonite in precipitated form similar to Zn-Al hydrotalcite-like compound (HTlc) regardless of CTC presence.

The adsorption behavior of bisphenol S (BPS) on reduced graphene oxide (rGO) was investigated. The adsorption kinetics data are best described with a pseudo-second-order model and the equilibrium data are well fitted by both Freundlich and Langmuir models. The maximum adsorption capacity of BPS on rGO at pH 6.0 and T = 298 K was 261.74 mg g−1. It was found that the increase of solution pH was unfavorable for BPS adsorption due to the increasing electrostatic repulsion between BPS and rGO. The thermodynamics data indicated that the adsorption of BPS on rGO was a spontaneous and exothermic process. Fourier transform infrared (FTIR) spectra suggested that BPS adsorption on rGO was primarily driven by π–π interaction between the graphene's hexagonal arrays and the aromatic core of BPS. Results from this study demonstrate that rGO is a promising adsorbent for BPS removal in water treatment.

The adsorption kinetics, isotherms and thermodynamics of Cr(III) on graphene oxide (GO) were studied. The adsorption kinetic data were well described with pseudo-second-order model and the equilibrium data were well fitted by Langmuir model. The calculated thermodynamic parameters indicated that the adsorption of Cr(III) on GO was spontaneous and endothermic. The maximum adsorption capacity of Cr(III) on GO at pH 5.0 and T=296 K was about 92.65 mg g(-1), which was higher than other reported adsorbents. It was found that the adsorption of Cr(III) on GO was strongly dependent on solution pH, but weakly dependent on ionic strength. Fourier transform infrared (FTIR) spectra suggested that Cr(III) was adsorbed on GO mainly through the formation of inner-sphere complexes with the O-containing functional groups on GO surface. Results in this study suggested that GO was a suitable material for the preconcentration and removal of Cr(III) from water. (C) 2014 Elsevier B.V. All rights reserved.

The effects of humic acid (HA) on copper (Cu(II)) adsorption onto few-layer reduced graphene oxide (FRGO) and few-layer graphene oxide (FGO) were investigated using a batch equilibration method, micro-Fourier transform infrared spectroscopy, and extended X-ray absorption fine structure spectroscopy (EXAFS). The results showed that HA was adsorbed on FRGO through it-it interaction. The adsorbed HA introduced O-containing functional groups and negative charges to FRGO surfaces, increasing Cu(II) adsorption through chemical complexation and electrostatic attraction. In contrast, HA was adsorbed onto FGO mainly through polar interactions, due to its rich O-containing functional groups. The adsorbed HA had little effect on Cu(II) adsorption onto FGO because the shielding effect of HA on Cu(II) adsorption was offset by newly introduced adsorption sites of HA on FGO. EXAFS results suggested that Cu(II) was adsorbed on FRGO and FGO mainly through the coordination with their O-containing functional groups. When HA was added at pH 4.0 and 6.0, more Cu(II) was adsorbed on HA-coated FRGO. At pH 8.0, a portion of Cu(II) in solution precipitated on FRGO surface, while the presence of HA led to the formation of FRGO-HA-Cu ternary surface complexes instead of Cu(II) precipitation. (C) 2014 Elsevier Ltd. All rights reserved.

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(+), Zn(2+), and Al(3+)) 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 Zn(2+) and Al(3+) reduced TCP adsorption onto ash. The desorption of TCP from ash showed obvious hysteresis, and the presence of Ag(+), Zn(2+), and Al(3+) caused the desorption to be less hysteretic. The suppression of TCP adsorption by Zn(2+) and Al(3+) was ascribed to the partial overlapping of adsorption groups between TCP and metal ions. Al(3+) had a stronger inhibition effect than that of Zn(2+) due to its higher binding capacity and larger hydrated ionic radius than those of Zn(2+). 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 Ca(2+), 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.

Multi-walled carbon nanotubes (MWCNTs) are superadsorbents for perfluorooctane sulfonate (PFOS) and heavy metals, which coexist in wastewater. The interaction between PFOS and Cu(II) with regard to their adsorption and desorption on MWCNTs was evaluated in this study. The adsorption of PFOS on MWCNTs enhanced with an increase of Cu(II). Desorption of PFOS showed no hysteresis without Cu(II), while pronounced hysteresis with Cu(II). Increases of the adsorption and the occurrence of desorption hysteresis of PFOS in the presence of Cu(II) may due to the PFOS adsorption via a Cu(II) bridge. The adsorption of Cu(II) increased with an increase of PFOS. The desorption hysteresis factors in the presence of PFOS were lower than those in the absence of PFOS. Increases of the adsorption and decreases of desorption hysteresis factors may be attributed to the Cu(II) adsorption via a PFOS bridge. Results obtained by X-ray absorption spectroscopy verified the formation of inner-sphere complexes between Cu(II) and functional groups of MWCNTs without PFOS, while out-sphere complexes with large amount of PFOS. The effect of Cu(II) and PFOS adsorption on the zeta potential of MWCNTs was also studied. The results showed that the coexistence of Cu(II) and PFOS greatly affects their sorption and desorption behaviors on MWCNTs thereby their fate and transport in wastewater. (C) 2012 Elsevier B.V. All rights reserved.

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(+).

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. (C) 2011 Elsevier B.V. All rights reserved.

The mutual effects of metal cations (Cu(2+), Pb(2+), Zn(2+), and Cd(2+)) and p-nitrophenol (NP) on their adsorption desorption behavior onto wheat ash were studied. Results suggested that Cu(2+), Pb(2+), and Zn(2+) diminished the adsorption and increased the desorption of NP remarkably, while Cd(2+) had no such effect. In contrast, NP diminished the adsorption of Cu(2+), Pb(2+), and Zn(2+) 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 Cu(2+), Pb(2+), and Zn(2+) shells occupied the surface of ash and prevent nonspecific adsorption of NP onto ash surface; (2) Cu(2+), Pb(2+), and Zn(2+) may block the micropores of ash, resulting in decreased adsorption of NP; (3) complexation of Cu(2+), Pb(2+), and Zn(2+) 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", Cd(2+) is less efficient in the complexation of oxygen-containing acid groups than Cu(2+), Pb(2+), and Zn(2+). Thus, Cd(2+) had no effect on the adsorption of NP on wheat ash.

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.

Effects of copper (Cu) and aluminum (Al) on the adsorption of sulfathiazole (STZ) and tylosin (T) to peat and soil were investigated using a batch equilibration method. Results show that Cu suppressed STZ adsorption onto peat and soil at pH 5.0 because of the electrostatic competition, while increased STZ adsorption at pH 5.0 due to the formation of STZ-Cu complexes and/or Cu bridge. In contrast, Al only decreased STZ adsorption at pH 6.0, and exerted slight effect on STZ adsorption at6.0. As for T, both Cu and Al suppressed its adsorption over the entire pH range owing to three reasons: 1) electrostatic competition between Cu/Al and T(+); 2) Cu/Al adsorption made the soil and peat surface less negatively charged, which was unfavorable for T(+) adsorption; 3) the shrunken pore size of peat and soil retarded the diffusion of large-sized T into these pores.

The coadsorption of ciprofloxacin (Cip) and Cu(II) on montmorillonite and kaolinite was studied between pH 4.0 and 9.5. At pH5.0, 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 pH6.0 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 pH7.0, 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 kaolinite's 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 pH8.0, 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).

The effects of copper (Cu2+), lead (Pb2+), and cadmium (Cd2+) on the sorption of 2,4,6-trichlorophenol (TCP) to and desorption from wheat ash and two commercial humic acids were studied. Copper and Pb2+ diminished the sorption of TCP onto all adsorbents, and made desorption of TCP less hysteretic from ash and German humic acids (GeHA), but more hysteretic from Tianjin humic acids (TJHA). Cadmium had little effect on TCP sorption and desorption. Fourier-transform infra red (FTIR) and X-ray absorption spectroscopy (XAS) in conjunction with fluorescence quenching studies provided insights into the mechanisms of TCP sorption and desorption as affected by Cu2+ and Pb2+, indicating that complexation of Cu2+ and Pb2+ was likely via carboxylic, hydroxylic and phenolic groups of ash, TJHA and GeHA, and that theses same functional groups also reacted with TCP during sorption. In contrast, Cd, a "soft acid", had no effect on the adsorption of TCP. Hydration shells of dense water around adsorbed Cu2+ and Pb2+ ions may also compete with TCP for available surface area. Fluorescence quenching of pyrene verified that for TJHA, Cu2+ and Pb2+ promoted the formation of supramolecular associations with interior hydrophobic regions separated from aqueous surroundings by exterior hydrophilic layers.

There are currently few studies on the dual effects of metal ions on the sorption of atrazine and conversely of atrazine on metal adsorption on multiwalled carbon nanotubes (MWCNTs). While a number of sorption models were considered to describe the sorption of atrazine on MWCNTs, the Polanyi-Manes model (PMM) fit the sorption isotherms well with the lowest mean weighted square errors. Atrazine was mainly adsorbed onto the surface and micropores of MWCNTs bundles or aggregates. Hydrogen bonding between azo and amino nitrogen of atrazine and functional groups on MWCNTs also occurred. Oxygenated functionalities, mainly carboxylic groups on MWCNTs surface, decreased the sorption of atrazine. Metal cations Cu2+, Pb2+, and Cd2+ diminished the sorption of atrazine depending on the oxygenated functionalities densities. The mechanisms ascribed were due to the formation of surface or inner-sphere complexes of Cu2+, Pb2+, and Cd2+ through carboxylic groups and hydration, which may occupy part of the surface of MWCNTs-O. The large hydration shell of metal cations may intrude or shield the hydrophobic and hydrophilic sites and indirectly compete with atrazine for surface sites, leading to the inhibition of atrazine adsorption around the metal-complexed moieties.

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. (C) 2009 Elsevier Ltd. All rights reserved.

Adsorption of cationic methylene blue and anionic orange II onto unmodified and surfactant-modified zeolites was studied using a batch equilibration method. The effects of equilibrium time, solution pH, and sorption temperature were examined. The results suggested that 2% sodium dodecyl benzenesulfonate (SDBS)- and 3% sodium dodecyl sulfate (SDS)-modified zeolites had higher adsorption capacities for methylene blue than the unmodified zeolite, while 2% cetylpyridinium bromide hexadecyl (CPB)- and 2% hexadecylammonium bromide (HDTMA)-modified zeolites were the best adsorbents for orange II. The adsorption conditions were optimized, and the mechanisms of adsorption are briefly discussed.

The effect of cationic copper (Cu2+) on the sorption of anionic metsulfuron-methyl (Me) and cationic difenzoquat (DZ) to peat and soil was studied using a batch equilibration method. The results showed that Cu2+ increased the sorption of Me but diminished the sorption of DZ. The adsorption of Cu2+ on the surface of peat and soil neutralizes the negative charge, making the zeta potential (zeta) of peat and soil less negative, consequently decreasing the repulsion between the surface of peat or soil and Me and increasing the sorption of Me. Cu2+ may additionally form Cu-Me complexes in aqueous solution, which was preferentially sorbed to peat and soil over the anionic Me. In contrast, the decreased negative surface charge of soil and peat does not favor the sorption of cationic DZ. Fourier transform infrared showed that DZ may be sorbed through interaction with -OH or -COOH groups of peat and soil and that surface complexes of Cu2+ may form through these groups. A competitive sorption between Cu2t and DZ for the same sorption sites is indicated, leading to mutual sorption inhibition of both cations.

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 or p-nitrophenol was sorbed previously, or the soil colloidal phase was removed in part previously. The results suggested that Cu suppressed the sorption of p-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.

The effect of lead on the sorption of 2,4,6-trichlorophenol (2,4,6-TCP) on soil and peat was investigated using a batch equilibration method. Lead markedly diminished the sorption of 2,4,6-TCP, and 2,4,6-TCP had little effect on lead sorption. Peat was a more effective adsorbent for 2,4,6-TCP than soil. The desorption hysteresis of 2,4,6-TCP verified the presence of high-energy sorption sites. Mechanisms of lead suppression effect on the 2,4,6-TCP sorption included the following: Firstly, lead accelerated the aggregation of colloids, the aggregates covered the surface in part and shrunk the pore sizes of the adsorbents, hence decreased the sorption of 2,4,6-TCP. Secondly, X-ray absorption and Fourier transform infrared spectroscopy study suggested that lead competed with 2,4,6-TCP for carboxylic, phenolic and Si-OH groups of organic matter and clay minerals. Such competition was partly responsible for the overall suppression effect of lead on the sorption of 2,4,6-TCP.

The effect of copper on adsorption of p-nitrophenol on two typical Chinese soils was investigated using a batch-equilibration method. Adsorption experiments were carried out when both copper and p-nitrophenol were adsorbed Simultaneously, and when copper was previously adsorbed oil soils. It was observed that adsorption of p-nitrophenol decreased with increasing copper concentrations thereby indicating a competition between copper and p-nitrophenol for occupying the adsorption sites oil soils. Moisture increased the hydrated sphere and the acidity of Water Surrounding the cation, which further reduced the adsorption of p-nitrophenol. Fourier transform infrared Spectroscopy study provided the direct evidence for the coordination of p-nitrophenol sorbed by soils with metal cation in n-hexane system. It was observed that the perturbations included a red shift of the v(sym) (NO) hand, a concomitant blue-shift of the v(sym) (NO) hand and a blue-shift of C-N hand when compared with the infrared spectra obtained from water solution. (c) 2005 Elsevier Ltd. All rights reserved.

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.