Synthesis and application of Cu-BTC@ZSM-5 composites as effective adsorbents for removal of toluene gas under moist ambience: kinetics,thermodynamics, and mechanism studies

Metal organic frameworks (MOFs) are excellent adsorbents that provide abundant specific surface area, adjustable pore structure, and rich active sites. The purpose of this study was to prepare composites with hydrophobic and high microporous specific surface area and to adsorb toluene gas in moist ambience. An ethanol activation-assisted hydrothermal method was proposed to synthesize copper-benzene-1,3,5-tricarboxylic acid (Cu-BTC) metal-organic framework, Cu-BTC, and ZSM-5 molecular sieve composites (Cu-BTC@ZSM-5). The dynamic adsorption process of toluene on different adsorbents was investigated, and the results showed that the toluene adsorption capacity of Cu-BTC@ZSM-5 (158.6 mg/g) was 2.53 times higher than Cu-BTC (62.7 mg/g), when the ZSM-5 content is 5% and the humidity is 30%RH. Compared with other factors, the humidity inhibited the adsorption of toluene on Cu-BTC@ZSM-5. Langmuir model and the pseudo-second kinetics model can better describe the adsorption behavior of Cu-BTC@ZSM-5. The thermodynamic results showed the adsorption process was a spontaneous exothermic process at low temperature and mainly physical adsorption. The relative regenerability can still up to 80.4% after six cycles. The adsorption mechanisms of Cu-BTC@ZSM-5 were pore-filling adsorption, π-π interaction, cation-π bonding, and hydrophobic interactions. This study will help to design a systematic route to evaluate the adsorption performance of Cu-BTC@ZSM-5 for toluene.

     

Modeling competitive adsorption of molybdate, sulfate, selenate, and selenite using a Freundlich-type multi-component isotherm

This study examined the interactions of MoO4(2-) + SO4(2-), MoO4(2-) + SeO4(2-), and MoO4(2-) + SeO3(2-) systems on gamma-Al2O3 to better understand the competitive adsorption of these anions in the natural environment. The Freundlich isotherms of anionic adsorption onto gamma-Al2O3 in single and binary solutes were also investigated to estimate the competition between these anions. Experimental results indicate that a higher concentration of competitive solute yields a higher efficiency of the competitive solute's prevention of MoO4(2-) adsorption. The most significant result was found in the MoO4(2-) + SeO3(2-) system. The Freundlich isotherm constant (n) increases with the competitive solute concentration. The suitability of a Freundlich-type isotherm, the Sheindorf-Rebuhn-Sheintuch (SRS) equation, and the modified SRS equation in representing the competitive adsorption of MoO4(2-), SO4(2-), SeO4(2-), and SeO3(2-) on gamma-Al2O3 surface, was also examined. Each set of isotherm data was found to conform to linear SRS expressions, allowing competition coefficients to be derived on a concentration basis for each binary-solute system. The competition coefficient aij and relative affinity coefficients alphaij can be seen as a way to quantify competitive interactions. The proposed SRS and modified SRS equations are simple mathematical expressions accounting for competitive interactions of anions present in a mixture for the range of concentrations over which each individual component exhibits Freundlich behavior.     

三氯乙酸与其他有机物在活性炭上的竞争吸附

通过等温吸附实验,考察了三氯乙酸(TCAA)与十二烷基苯磺酸钠(DBS)、腐殖酸(HA)在活性炭(GAC)上的竞争吸附现象。结果表明,GAC对TCAA的吸附符合Langmuir模型,对DBS和HA的吸附均符合Freudlich模型;在GAC上,DBS和HA对TCAA构成竞争吸附,大分子HA阻塞GAC的微孔,使得TCAA与DBS难以进入微孔;GAC对3种物质的吸附能力由大到小依次为DBS、TCAA和HA;离子型表面活性剂DBS憎水性一端与TCAA竞争吸附位,亲水性一端与TCAA形成吸附,使GAC总饱和吸附量有所加大。     

Cosorption of organic chemicals with different properties: their shared and different sorption sites

Complementary sorption of different chemicals was expected and investigating the relationship between the sorption inhibition of primary sorbate (ΔQ(pri)) and sorption of secondary sorbate (Q(sec)) could provide a new angle to understand coadsorption of different chemicals. This study used bisphenol A (BPA) as the primary adsorbate, sulfamethoxazole (SMX) as the competitor, and carbon nanotubes as model adsorbents to study their complementary and competitive adsorption. At low BPA concentrations, the sorption of SMX (Q(sec)) exceeded BPA sorption inhibition (ΔQ(pri)), indicating that these two chemicals complementarily adsorbed on their respectively preferred sorption sites. At high BPA concentrations, higher ΔQ(pri) was observed in comparison to Q(sec), which may be resulted from different packing efficiencies of the adsorbed SMX and BPA. This study emphasized that both competitive and complementary sorption should be discussed in binary sorption system.     

Preparation of various thiol-functionalized carbon-based materials for enhanced removal of mercury from aqueous solution

In this work, biochar (BC), activated carbon (AC), and graphene oxide (GO) were thiol-functionalized using 3-mercaptopropyltrimethoxysilane (3-MPTS) (named as BCS, ACS, and GOS, respectively). BCS, ACS, and GOS were synthesized mainly via the interaction between hydrolyzed 3-MPTS and surface oxygen-containing functional groups (e.g., –OH, O–C=O, and C=O) and π-π interaction. The materials before and after modification were characterized and tested for mercury removal, including sorption kinetics and isotherms, the effects of adsorbent dosage, initial pH, and ionic strength. Pseudo-second-order sorption kinetic model (R² = 0.992~1.000) and Langmuir sorption isotherm model (R² = 0.964~0.998) fitted well with the sorption data of mercury. GOS had the most –SH groups with the largest adsorption capacity for Hg²⁺ and CH₃Hg⁺ (449.6 and 127.5 mg/g), followed by ACS (235.7 and 86.7 mg/g) and BCS (175.6 and 30.3 mg/g), which were much larger than GO (96.7 and 4.9 mg/g), AC (81.1 and 24.6 mg/g), and BC (95.6 and 9.4 mg/g). GOS and ACS showed stable mercury adsorption properties at a wide pH range (2~9) and ionic strength (0.01~0.1 mol/L). Mercury maybe removed by ligand exchange, surface complexation, and electrostatic attraction.

     

Modeling adsorption in multicomponent systems using a Freundlich-type isotherm

The suitability of a Freundlich-type isotherm, the Sheindorf-Rebuhn-Sheintuch (SRS) equation, to represent the competitive adsorption of Sr, Cs and Co in Ca-montmorillonite suspensions was investigated. Experimental adsorption data were obtained for systems containing these cations as single-component, binary and ternary mixtures. The competition coefficient α_ij, which were obtained based on the experimental adsorption data for bicomponent systems, can be viewed as a way to quantify competitive interactions. The competition coefficients obtained for the cations under consideration indicate that their competitive interactions are of similar magnitude, with the cation least affected by competitive effects being Cs, while the adsorption of Co was more significantly affected by the presence of Cs, and Sr by the presence of Co. After α_ij-values were substituted in the SRS equation, the adsorption of systems of three or more components could be predicted. To validate the SRS equation, the adsorption values predicted by this equation for the ternary mixture Sr---Cs--- Co were compared to values determined experimentally. The SRS equation successfully modeled adsorption for the range of concentrations that followed Freundlich behavior.     

Comparative and competitive adsorption of Cr(VI), As(III), and Ni(II) onto coconut charcoal

This study evaluates the behavior of coconut charcoal (AC) to adsorb Cr(VI), As(III), and Ni(II) in mono- and multicomponent (binary and ternary) systems. Batch experiments were carried out for mono- and multicomponent systems with varying metal ion concentrations to investigate the competitive adsorption characteristics. The adsorption kinetics followed the mechanism of the pseudo-second-order equation in both single and binary systems, indicating chemical sorption as the rate-limiting step of adsorption mechanism. Equilibrium studies showed that the adsorption of Cr(VI), As(III), and Ni(II) followed the Langmuir model and maximum adsorption capacities were found to be 5.257, 0.042, and 1.748 mg/g, respectively. In multicomponent system, As(III) and Ni(II) adsorption competed intensely, while Cr(VI) adsorption was much less affected by competition than As(III) and Ni(II). With the presence of Cr(VI), the adsorption capacities of As(III) and Ni(II) on AC were higher than those in single system and the metal sorption followed the order of Ni(II)?>?As(III)?>?Cr(VI). The results from the sequential adsorption–desorption cycles showed that AC adsorbent held good desorption and reusability.     

Evaluation of the multiple-ion competition in the adsorption of As(V) onto reclaimed iron-oxide coated sands by fractional factorial design

This study describes the competitive effects of selected ions and natural organic matter on As(V) removal using reclaimed iron-oxide coated sands (RIOCS) in the single- and multi-ion systems. A 2(7-3) factional factorial experimental design (FFD) was employed for screening main competitive factors in this adsorption process. As a result, the inhibitive competition effects of the anions on As(V) removal in the single ion system were in the following sequence: PO(4)(3-)>SiO(3)(2-)>HCO(3)(-)>humic acid (HA)>SO(4)(2-)>Cl(-), whereas the cation Ca(2+) was observed to enhance the As(V) removal. In addition, the optimum initial pH for As(V) removal in single-ion system was 5. Based on the estimates of major effects and interactions from the FFD, PO(4)(3-), SiO(3)(2-), Ca(2+) and HA were important factors on As(V) removal in the multi-ion system. The promoters for the As(V) removal were found to be Ca(2+) and, to a lesser extent, SO(4)(2-). The competitive effects of these ions on As(V) removal were in the order of PO(4)(3-), SiO(3)(2-), HA, HCO(3)(-), and Cl(-). In the single ion system, the efficiencies of As(V) removal range from 75% to 96%, much higher than those in the multi-ion system (44%) at the initial pH 5. Clearly, there were some complex anion interactions in the multi-ion system. To promote the removal of As(V) by RIOCS, it is proposed to lower the pH in the single-ion system, while in the multi-ion system, the increase of the Ca(2+) concentration, or decreases of PO(4)(3-), SiO(3)(2-) and HA concentrations is suggested.     

Effects of compositional heterogeneity and nanoporosity of raw and treated biomass-generated soot on adsorption and absorption of organic contaminants

A biomass-generated soot was sequentially treated by HCl-HF solution, organic solvent, and oxidative acid to remove ash, extractable native organic matter (EOM), and amorphous carbon. The compositional heterogeneity and nano-structure of the untreated and treated soot samples were characterized by elemental analysis, thermal gravimetric analysis, BET-N₂ surface area, and electron microscopic analysis. Sorption properties of polar and nonpolar organic pollutants onto the soot samples were compared, and individual contributions of adsorption and absorption were quantified. The sorption isotherms for raw sample were practically linear, while were nonlinear for the pretreated-soot. The removal of EOM enhanced adsorption and reduced absorption, indicating that EOM served as a partitioning phase and simultaneously masked the adsorptive sites. By drastic-oxidation, the outer amorphous carbon and the inner disordered core of the soot particles were completely removed, and a fullerene-like nanoporous structure (aromatic shell) was created, which promoted additional π-π interaction between phenanthrene and the soot.     

Mechanisms of competitive adsorption of Pb, Cu, and Cd on peat

Combined use of batch equilibration adsorption and X-ray absorption spectroscopy (XAS) was employed to study the mechanisms of competitive adsorption of Pb, Cu, and Cd on Danish and Heilongjiang peat in single- and multi-solute systems. The adsorption capacity and initial adsorption rate on the same peat in single-solute systems followed the order Pb>Cu>Cd. Both the adsorbed amount of each metal (q'm) and its initial adsorption rate were decreased in multi-solute systems. It was observed that the adsorbed amounts of metals at low-energy adsorption sites (qm,1) decreased pronouncedly compared to those at high-energy adsorption sites (qm,2), indicating that the competitive adsorption of Pb, Cu and Cd occurred mainly at the low-energy adsorption sites. XAS study revealed that both Pb and Cu were coordinated in peat predominantly to carboxylic moieties without excluding the hydroxyl groups, thereby providing an insight into the mechanism of competitive adsorption of Pb and Cu on peat.     

Removal of the emerging contaminant bisphenol A by an ureasil–PEO hybrid membrane: experimental study and molecular dynamic simulation

This work reports the use of a cross-linked ureasil–PEO hybrid matrix (designated PEO800) as an efficient adsorbent to retain the emerging contaminant bisphenol A (BPA) from an aqueous medium. The in-deep experimental and theoretical results provide information about the interactions between PEO800 and BPA. The in situ UV-vis spectroscopy data and the pseudo-first order, pseudo-second order, Elovich, and Morris–Webber intraparticle diffusion models allowed us to propose a three-step mechanism for the adsorption of BPA onto PEO800. The results indicate that the pseudo-first-order kinetic model effectively describes the adsorption of BPA onto PEO800. Differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy confirmed the interaction of PEO800 with BPA, showing an alteration in the chemical environment of the polymer ether oxygen atoms present in the hybrid matrix. The molecular dynamic simulation provides further evidence that the BPA molecules interact preferentially with PEO. The amount of desorbed BPA depended on the pH and solvent used in the assays. This work provides new opportunities for using the hydrophilic ureasil–PEO matrix which has demonstrated its abilities in being a fast and easy alternative to successfully removing organic contaminants from aqueous mediums and therefore having potential applications in water remediation.

Graphical abstract

     

Enhanced removal of humic acid from micro-polluted source water in a surface discharge plasma system coupled with activated carbon

Surface discharge plasma (SDP) combined with activated carbon (AC) was employed to eliminate dissolved organic matter from micro-polluted source water, with humic acid (HA) as the model pollutant. Synergistic effect on HA removal was observed in the SDP-AC system; HA removal efficiency reached 60.9% within 5-min treatment in the SDP-AC system with 5.0 g AC addition, whereas 16.7 and 17.4% of HA were removed in sole SDP system and AC adsorption, respectively. Scanning electron microscope and Boehm titration analysis showed that chemical reactions between active species and functional groups of AC occurred. The existence of isopropanol or benzoquinone exhibited inhibitive effects on HA removal in the SDP system, while these inhibitive effects were weakened in the SDP-AC system. The influences of AC on ozone equivalent concentration and H₂O₂ concentration were evaluated, and there were approximately 39 and 20% decline in ozone equivalent concentration and H₂O₂ concentration within 6-min treatment in the SDP-AC system, respectively, compared with those in the sole SDP system. Dissolved organic carbon, specific ultraviolet absorbance, and UV absorption ratios analysis demonstrated that the SDP treatment destroyed the chromophoric groups, double bonds, and aromatic structure of HA molecules, and these destructive actions were strengthened by AC.     

Arsenite oxidation and arsenic adsorption on birnessite in the absence and the presence of citrate or EDTA

Birnessite not only oxidizes arsenite into arsenate but also interacts with organic matter in various ways. However, effects of organic matter on interaction between As and birnessite remain unclear. This study investigated effects of citrate and EDTA (3.12 and 2.05 mM, respectively) on oxidation of As(III) (1.07 mM) and adsorption of As(V) (0.67 mM) on birnessite (5.19 mM as Mn) at near-neutral pH. We found that As(V) adsorption on birnessite was enhanced by citrate and EDTA, which resulted from the increase in active adsorption sites via dissolution of birnessite. In comparison with citrate batches, more As was adsorbed on birnessite in EDTA batches, where dissolved Mn was mainly presented as Mn(III)-EDTA complex. Citrate or EDTA-induced dissolution of birnessite did not decrease the As(III) oxidation rate in the initial stage where As(III) oxidation rate was rapid. Afterwards, As(III) oxidation was conspicuously suppressed in citrate-amended batches, which was mainly attributed to the decrease in adsorption sites by adsorption of citrate/Mn(II)-citrate complex. This suppression was enhanced by the increase in concentrations of dissolved Mn(II). Citrate inhibited As adsorption after As(III) oxidation due to the strong competitive adsorption of citrate/Mn(II)-citrate complex. However, the As(III) oxidation rate was increased in EDTA-amended batches in the late stage, which mainly derived from the increase in the active sites via birnessite dissolution. The strong complexation ability of EDTA led to formation of Mn(III)-EDTA complex. Arsenic adsorption was not affected due to the limited competitive adsorption of the complex on the solid. This work reveals the critical role of low molecular weight organic acids in geochemical behaviors of As and Mn in aqueous environment.

     

Adsorption of sulfamethoxazole on functionalized carbon nanotubes as affected by cations and anions

The environmental risks of antibiotics have attracted lots of research attention, but their environmental behavior is not clear yet. Functionalized carbon nanotubes (CNTs) were used as model adsorbents and sulfamethoxazole (SMX) was used as a model antibiotic to investigate the effect of both cations (Ca²⁺, Cs⁺) and anions (phosphate) on antibiotics adsorption. Various mechanisms (such as electrostatic interaction, hydrophobic interaction, π-π and hydrogen bonds) play roles in SMX adsorption. Cations and anions could “wedge into” these mechanisms and thus alter SMX adsorption. This study emphasized that both increased and decreased SMX adsorption could be observed with the addition of cations/anions, depending on environmental conditions (such as pH in this current study). The net effect is the balance between the increased and decreased effects. The contribution of different mechanisms to the overall antibiotic adsorption on solid particles should be identified to accurately predict the apparent effect by cations and anions.     

Geochemistry of inorganic arsenic and selenium in a tropical soil: effect of reaction time, pH, and competitive anions on arsenic and selenium adsorption

Factors that can affect As and Se adsorption by soils influence the bioavailability and mobility of these elements in the subsurface. This research attempted to compare the adsorption capacities of As(III), As(V), Se(IV), and Se(VI) on a tropical soil commonly found in Singapore in a single-species system. The effect of reaction time, pH, and competitive anions at different concentrations on the adsorption of both As and Se species were investigated. The As and Se adsorption isotherm were also obtained under different background electrolytes. The batch adsorption experiments showed that the sequence of the As and Se adsorption capacities in the soil was As(V) > Se(IV) > As(III) > Se(VI). The adsorption kinetics could be best described by the Elovich equation. The adsorption of As(V), Se(IV), and Se(VI) appeared to be influenced by the variable pH-dependent charges developed on the soil particle surfaces. Phosphate had more profound effect than SO4(2-) on As and Se adsorption in the soil. The competition between PO4(3-) and As or Se oxyanions on adsorption sites was presumably due to the formation of surface complexes and the surface accumulation or precipitation involving PO4(3-). The thermodynamic adsorption data for As(V) and Se(IV) adsorption followed the Langmuir equation, while the As(III) and Se(VI) adsorption data appeared to be best-represented by the Freundlich equation.     

Engineered biochar composites with zeolite,silica, and nano-zerovalent iron for the efficient scavenging of chlortetracycline from aqueous solutions

Date palm waste–derived biochar (DBC) was produced through pyrolysis (600 °C) and modified with zeolite (Z-DBC), silica (S-DBC), or nano-zerovalent iron (nZVI-DBC) to design efficient sorbents. The pristine and engineered biochars were characterized by SEM, XRD, BET, TGA, CHNS-O, and FTIR to investigate the surface, structural, and mineralogical composition. The nZVI-DBC exhibited lowest pH (6.15) and highest surface area (220.92 m² g⁻¹), carbon (80.55%), nitrogen (3.78%), and hydrogen (11.09%) contents compared with other biochars. Isotherm sorption data for chlortetracycline (CTC) removal from aqueous solutions was described well by Langmuir and Redlich–Peterson isotherms showing the highest fitness (R² values in the range of 0.88–0.98 and 0.88–0.99, respectively). Langmuir predicted maximum CTC adsorption capacity was in order of nZVI-DBC (89.05 mg g⁻¹) > S-DBC (45.57 mg g⁻¹) > Z-DBC (30.42 mg g⁻¹) > DBC (28.19 mg g⁻¹). Kinetics adsorption data was best described by power function model (R² = 0.93–0.99), followed by interaparticle diffusion (R² = 0.85–0.96) model. The nZVI-DBC performed outclass by removing 98% of CTC, followed by S-DBC (68%), Z-DBC (35%), and DBC (36%). Chemisorption, H-bonding, and interaparticle diffusion were the operating mechanisms for CTC adsorption onto DBC, S-DBC, and Z-DBC, while π-π electron donor–accepter interactions and redox reactions augmented these mechanisms for highest CTC adsorption onto nZVI-DBC. Therefore, nZVI-DBC may serve as an efficient green technology for the removal of CTC from aqueous solutions and to reduce surface date palm waste pollution.

.

     

Competing TCE and cis-DCE degradation kinetics by zero-valent iron-experimental results and numerical simulation

The successful dechlorination of mixtures of chlorinated hydrocarbons with zero-valent metals requires information concerning the kinetics of simultaneous degradation of different contaminants. This includes intraspecies competitive effects (loading of the reactive iron surface by a single contaminant) as well as interspecies competition of several contaminants for the reactive sites available. In columns packed with zero-valent iron, the degradation behaviour of trichloroethylene (TCE), cis-dichloroethylene (DCE) and mixtures of both was measured in order to investigate interspecies competition. Although a decreasing rate of dechlorination is to be expected, when several degradable substances compete for the reactive sites on the iron surface, TCE degradation is nearly unaffected by the presence of cis-DCE. In contrast, cis-DCE degradation rates decrease significantly when TCE is added. A new modelling approach is developed in order to identify and quantify the observed competitive effects. The numerical model TBC (Transport, Biochemistry and Chemistry, Sch?fer et al., 1998a) is used to describe adsorption, desorption and dechlorination in a mechanistic way. Adsorption and degradation of a contaminant based on a limited number of reactive sites leads to a combined zero- and first-order degradation kinetics for high and low concentrations, respectively. The adsorption of several contaminants with different sorption parameters to a limited reactive surface causes interspecies competition. The reaction scheme and the parameters required are successfully transferred from Arnold and Roberts (2000b) to the model TBC. The degradation behaviour of the mixed contamination observed in the column experiments can be related to the adsorption properties of TCE and cis-DCE. By predicting the degradation of the single substances TCE and cis-DCE as well as mixtures of both, the calibrated model is used to investigate the effects of interspecies competition on the design of permeable reactive iron barriers. Even if TCE is present in only small concentrations (>3% of molar cis-DCE concentration) it is the contaminant limiting the residence time and the required thickness of the iron barrier.     

Modeling the competitive effect of phosphate, sulfate, silicate, and tungstate anions on the adsorption of molybdate onto goethite

The mobility of Mo in soils and sediments depends on several factors including soil mineralogy and the presence of other oxyanions that compete with Mo for the adsorbent's retention sites. Batch experiments addressing Mo adsorption onto goethite were conducted with phosphate, sulfate, silicate, and tungstate as competing anions in order to produce competitive two anions adsorption envelopes, as well as competitive two anions adsorption isotherms. Tungstate and phosphate appear to be the strongest competitors of Mo for the adsorption sites of goethite, whereas little competitive effects were observed in the case of silicate and sulfate. Mo adsorption isotherm from a phosphate solution was similar to the one from a tungstate solution. The charge distribution multi-site complexation (CD-MUSIC) model was used to predict competitive adsorption between MoO(4)(2-) and other anions (i.e., phosphate, sulfate, silicate and tungstate) using model parameters obtained from the fitting of single ion adsorption envelopes. CD-MUSIC results strongly agree with the experimental adsorption envelopes of molybdate over the pH range from 3.5 to 10. Furthermore, CD-MUSIC prediction of the molybdate adsorption isotherm show a satisfactory fit of the experimental results. Modeling results suggest that the diprotonated monodentate complexes, FeOW(OH)(5)(-0.5) and FeOMo(OH)(5)(-0.5), were respectively the dominant complexes of adsorbed W and Mo on goethite 110 faces at low pH. The model suggests that Mo and W are retained mainly by the formation of monodentate complexes on the goethite surface. Our results indicate that surface complexation modeling may have applications in predicting competitive adsorption in more complex systems containing multiple competing ions.     

Effects of pre-oxidation and adsorption on haloacetonitrile and trichloronitromethane formation during subsequent chlorination

In this study, the effects of pre-oxidants permanganate (PM), persulfate (PS), hydrogen peroxide (PO), and ozone (OZ)) and/or adsorption on pseudoboemite-chitosan shell magnetic nanoparticles (ACMNs) on haloacetonitrile (HAN) and trichloronitromethane (TCNM) formation from aspartic acid (Asp; positive charge) and/or histidine (His; negative charge) were compared. Asp and His apparently do not interact in aqueous solution during chlorination. Asp and/or His can undergo partially oxidation by PM, but are recalcitrant to direct oxidation by PS and PO. Pre-oxidation with OZ decreases the formation of HANs but increases the formation of TCNM. ACMN prefers to adsorb Asp over His in the competitive sorption of coexisting Asp and His because of attractive electrostatic interactions. The rank order for the effect of the pre-oxidants and ACMN adsorption on dichloroacetonitrile and trichloroacetonitrile formation is OZ and ACMN adsorption > PM and ACMN adsorption > PS and ACMN adsorption > PO and ACMN adsorption; that for the effect of the pre-oxidants and ACMN adsorption on TCNM formation is PM and ACMN adsorption > PS and ACMN adsorption > PO and ACMN adsorption > OZ and ACMN adsorption. The favored adsorption of Asp over His by ACMN is weakened by pre-oxidation.

     

Adsorption of arsenic (V) on kaolinite and on kaolinite-humic acid complexes. Role of humic acid nitrogen groups

In order to investigate the influence of organic matter on arsenic retention, we used batch experiments at pH 7 to determine the adsorption of As(V) on three different solids: a crude, purified, Ca-exchanged kaolinite and two kaolinites coated with humic acids (HAs) having different nitrogen contents. We first examined the adsorption of each HA onto kaolinite, and then used the HA-kaolinite complexes to study As(V) adsorption. The results clearly show an influence of the HA coating on As adsorption. For example, with low initial As concentrations the solid/liquid partition coefficient (R(d)) for both HA complexes is greater than that for the crude kaolinite. We found that increasing the initial As concentrations decreased the R(d) values of the HA-coated kaolinites until finally they were the same as the crude kaolinite R(d) values. This suggests that adsorption occurs first on the HA sites and then, once the HA sites are saturated, on the remaining kaolinite sites. We also noted that the more reactive HA-kaolinite complex was the one with the highest N/C ratio. Comparing the amount of amine groups in the HA-kaolinite complexes with the total amount of adsorbed As indicates that the HA amine groups, due to their positive charge at pH 7, play a key role in the adsorption of As onto organic matter.