Removal of antibiotics, bacterial toxicity, and occurrence of antibiotic resistance genes in secondary hospital effluents treated with granular activated carbon and the impact of preceding chlorination.

This comprehensive investigation highlighted the complex adsorption behaviors of antibiotics onto granular activated carbon (GAC), the effectiveness of this adsorption in reducing bacterial toxicity, and the reduction of antibiotic resistance genes (ARGs) and antibiotic resistant bacteria (ARB) in hospital wastewater (HWW) effluents. Six GACs were characterized for their physicochemical properties, and their ability to adsorb six antibiotics in the background matrix of actual HWW was evaluated. Coconut shell-derived GAC (Co-U), which had the highest hydrophobicity and lowest content of oxygen-containing acidic functional groups, demonstrated the highest adsorption capacities for the tested antibiotics. Bacterial toxicity tests revealed that GACs could eliminate the bacterial toxicity from antibiotic intermediates present in chlorinated HWW. By contrast, the bacterial toxicity could not be removed by GACs in non-chlorinated HWW due to the greater presence of intermediate components identified by LC-MS/MS. The intraparticle diffusion coefficient of antibiotics adsorbed onto Co-U could be calculated by adsorption kinetics derived from the linear driving force model and the homogenous intraparticle diffusion model associated with the linear adsorption isotherms (0-150 µg/L). Meropenem and sulfamethoxazole exhibited the highest adsorption capacities in a single-solute solution compared to penicillin G, ampicillin, cetazidime, and ciprofloxacin. However, the greater adsorption capacities of meropenem and sulfamethoxazole disappeared in mixed-solute solutions, indicating the lowest adsorption competition. GAC can eliminate most ARGs while also promoting the growth of some ARB. Chlorination (free chlorine residues at 0.5 mg Cl2/L) did not significantly affect the overall composition of ARGs and ARB in HWW. However, the accumulation of ARGs and ARB on GAC in fixed bed columns was lower in chlorinated HWW than in non-chlorinated HWW due to an increase in the adsorption of intermediates.

Microplastics in retail shellfish from a seafood market in eastern Thailand: Occurrence and risks to human food safety.

This study aimed to investigate the presence of microplastics in three economically essential shellfish species: green mussels, cockles and spotted babylon. The average abundance of microplastics ranged from 2.41 to 2.84 particles/g wet weight. The predominant shape was fiber, with colors ranging from black-grey to transparent. The size of the microplastics discovered was <1.0 mm. Polystyrene and polyethylene were the most detected types in mussels and cockles, while linen was the predominant type in spotted babylon. The Thai population's estimated annual intake (EAI) of microplastics through shellfish consumption ranged from 20.23 to 1178.42 particles/person/year. The potential human health risks were evaluated using the polymer hazard index (PHI), which led to risk categories III-IV. These findings, along with others from the literature, indicate that shellfish consumption may pose risks to human health, depending on the species consumed and the origin of the specimens.

Amine-Functionalized Natural Rubber/Mesostructured Silica Nanocomposites for Adsorptive Removal of Clofibric Acid in Aqueous Phase.

This study is the first report on the synthesis, characterization and application of amine-functionalized mesoporous nanocomposites based on natural rubber (NR) and wormhole-like mesostructured silica (WMS). In comparison with amine-functionalized WMS (WMS-NH2), a series of NR/WMS-NH2 composites were synthesized via an in situ sol-gel method in which the organo-amine group was grafted onto the nanocomposite surface via co-condensation with 3-aminopropyltrimethoxysilane (APS) as the amine-functional group precursor. The NR/WMS-NH2 materials had a high specific surface area (115-492 m2 g-1) and total pore volume (0.14-1.34 cm3 g-1) with uniform wormhole-like mesoporous frameworks. The amine concentration of NR/WMS-NH2 (0.43-1.84 mmol g-1) was increased with an increase in the APS concentration, corresponding to high levels of functionalization with the amine groups of 53-84%. The H2O adsorption-desorption measurement revealed that NR/WMS-NH2 possessed higher hydrophobicity than WMS-NH2. The removal of clofibric acid (CFA), a xenobiotic metabolite of the lipid-lowering drug clofibrate, from the aqueous solution using WMS-NH2 and NR/WMS-NH2 materials was investigated using a batch adsorption experiment. The adsorption was a chemical process in which the pseudo-second order kinetic model expressed the sorption kinetic data better than the pseudo first-order and Ritchie-second kinetic order model. In addition, the CFA adsorption sorption equilibrium data of the NR/WMS-NH2 materials were fitted to the Langmuir isotherm model. The NR/WMS-NH2 with 5% amine loading had the highest CFA adsorption capacity (6.29 mg g-1).

Selective adsorption mechanisms of iodinated trihalomethanes onto thiol-functionalized HKUST-1s in a mixed solute.

The selective adsorption mechanisms involved in the competitive adsorption of five iodinated trihalomethanes (I-THMs) onto dithiolglycol and (3-mercaptopropyl)-trimethoxy functionalized HKUST-1 (HK-SH and HK-MPTS, respectively) were investigated by single- and mixed-batch adsorption. HK-SH had the highest adsorption rates and capacities for the five I-THMs, followed by HK-MPTS and pristine HKUST-1, even though the porosity and surface area decreased after modification. The primary adsorptive mechanism of HK-SH consists of ion-dipole interactions of I-THMs with the protonated hydroxyl and thiol groups at the metal (Cu) node, which is supported by Lewis acid-base reactions via Cu-Cu complex and π-π interactions. In a mixed solute, bromodiiodomethane, which was the most hydrophobic and had the smallest molecular size, exhibited the most competitive adsorption on HK-SH. In contrast, the selective adsorption of I-THMs onto HK-MPTS was affected by their log Kow values, causing hydrophobic partitioning onto the alkyl chain of the mercaptopropyl group. Iodinated haloforms tend to achieve a higher adsorption rate and capacity than chlorinated and brominated haloforms via hydrophobic partitioning. Moreover, dithiolglycol grafted onto HK-SH can better promote the excellent selective adsorption performance of iodoacetamide than dichloroiodomethane and iodoacetic acid in both single- and mixed-solute solutions due to hydrogen bonding via the -NH2 group of diiodoacetamide.

Reactivity characterization of SiO2-coated nano zero-valent iron for iodoacetamide degradation: The effects of SiO2 thickness, and the roles of dehalogenation, hydrolysis and adsorption.

The effect of SiO2-layer thickness in SiO2-coated nano zero-valent iron (nZVI) particles on the reactivity characteristics of iodoacetamide (IAcAm) degradation was evaluated. SiO2-layer thicknesses ranging from 3.6 to 27.3 nm were obtained through varying tetraethyl orthosilicate dosages of 0.001-1 M. The crystallinity, surface chemical composition, and physicochemical properties were evaluated for their effects on synergetic degradation mechanisms, dehalogenation, hydrolysis, and adsorption. At a thickness of 3.6 nm, the SiO2 layer offered the highest observed pseudo-first-order rate (kobs) and higher rates of IAcAm degradation were maintained under pH fluctuations (pH 5-7) and aerobic conditions compared to pristine nZVI. At this SiO2-layer thickness (3.6 nm), the rate of iron oxide-layer formation was reduced and the migration of reactive iron species (Fe0 and Fe2+) for the dehalogenation and hydrolysis reactions was enabled. In a single-solute solution, IAcAm elimination was greater than bromoacetamide and chloroacetamide elimination due to the weak ionic I-C bond. In mixed solute conditions, the hydrophobicity of chloroacetamide played a more significant role in competitive degradation through greater adsorption. The proportion of dehalogenation relative to hydrolysis during IAcAm degradation by pristine nZVI and SiO2-coated nZVI was approximately 0.6:0.4. Iodoacetic acid and acetic acid were detected as intermediates in the degradation pathway of IAcAm by pristine nZVI. In contrast, the SiO2 layer on nZVI can accelerate the transformation of IAcAm to acetamide and iodoacetic acid. The electrolyte background of tap water exhibited a slight inhibitory effect on the degradation of IAcAm for both nZVI and SiO2-coated nZVI.

Development of reactive iron-coated natural filter media for treating antibiotic residual in swine wastewater: Mechanisms, intermediates and toxicity.

Degradation mechanisms, surface phenomena, and the influence of co-existing organic matter on heterogeneous Fenton-like reactions were investigated using low-cost natural materials, to remove three veterinary antibiotics. Zeolite rock, laterite rock, and pumice rock were modified by adding ferric chloride. Fenton-like reactions yielded more than 50 % of antibiotic removal at a neutral pH. The modified zeolite exhibited the highest antibiotic removal efficiency. The heterogeneous Fenton-like reaction could be indicated by the simultaneous detection of Fe(II) and Fe(III) on the surface of the modified zeolite. Leaching iron was also observed to reduce the antibiotics with homogeneous Fenton-like reaction. The co-existing organic matter expressed by the COD below 400 mg/L did not have a considerable adverse impact on antibiotic removal. An H2O2 concentration as low as 20 µM was sufficient to react with the modified zeolite and degraded more than 70 % of the antibiotics at a neutral pH. The modified zeolite could be reused at least three times, with a removal efficiency of at least 80 %. The antibiotic degradation efficiencies in real treated swine wastewater were above 75 %. Moreover, the degradation intermediates and bacterial inhibition after treatment were investigated.

Evaluation of Fluoride Adsorption Mechanism and Capacity of Different Types of Bone Char.

The fluoride adsorption capacity of three types of bone char (BC), including cow BC (CBC), chicken BC (CKBC), and pig BC (PBC), was examined. At the optimum charring conditions (temperature and time), PBC had the highest hydroxyapatite (HAP) content (0.928 g-HAP/g-BC), while CBC had the highest specific surface area (103.11 m2/g-BC). CBC also had the maximum fluoride adsorption capacity (0.788 mg-F/g-HAP), suggesting that fluoride adsorption capacity depends more on the specific surface area of the BC than the HAP content. The adsorption data of CBC, CKBC, and PBC fit well with the pseudo-second-order model and the Langmuir isotherm. The maximum fluoride adsorption capacity of BC reached the maximum value when the solution had a pH of approximately 6.0. Lastly, the highest fluoride desorption occurred when the BCs were soaked in solutions with a pH higher than 11.0.

Adsorption of iodinated trihalomethanes onto thiol functionalized ZIF-8s: Active adsorption sites, adsorptive mechanisms, and dehalogenation by-products.

The adsorptive mechanisms operating in, and the effect of two different thiol modification methods on, the removal of five iodinated trihalomethanes (I-THMs) by the zeolite imidazolate framework (ZIF-8) were investigated in single and mixed solutions. The direct postgrafting of dithioglycol to the zinc complex node of ZIF-8 (ZF-SH) can increase the mesopore structures that enhance inner pore accessibility; this increase is a critical property required for excellent adsorption of I-THMs. The synergetic adsorptive interactions consist of Lewis acid-base interactions via the Zn-Zn complex, ion-dipole interactions involving the protonated hydroxyl and thiol groups, and hydrophobic interactions at the imidazole ring. In contrast to ZF-SH, the (3-mercaptopropyl)-trimethoxy functionalized silica coating on ZIF-8 (ZF-Si-SH) causes a lower thiol moiety and a steric effect that is reflected in its lower adsorption capacity. In both single and mixed solutions, the small molecular size and hydrophobic nature of I-THMs can promote better adsorption capacity on all thiol-modified ZIF-8, while the minus dipole charge distribution of the I-THMs structure plays a more critical role in selective adsorption on pristine ZIF-8. Interestingly, the dehalogenation of triiodomethane to diiodomethane due to a nucleophilic substitution (SN2) reaction can be accelerated by the thiol functionalized silica layer on ZIF-8.

Effects of electrolytes and fractionated dissolved organic matter on selective adsorption of pharmaceuticals on terephthalic acid-based metal-organic frameworks.

In this study, we investigated the synergetic effects of coexisting electrolytes and dissolved organic matter (DOM) on Carbamazepine (CBZ) and Ciprofloxacin (CIP) adsorption on the 1D flexible structure of MIL-53(Al) and 3D rigid structure of UiO-66(Zr). The effects of electrolytes on the adsorption of CBZ and CIP on 1D flexible framework of MIL-53(Al) were more significant than those observed from the 3D framework of UiO-66(Zr). The presence of sulfate, nitrate, and phosphate anions indicates high potential to promote the adsorption of CBZ and CIP onto MIL-53(Al) and UiO-66(Zr) because of the decrease of solubility and strengthening of electrostatic interactions by substitution of oxo-anions at the metal complex node via covalent bonding. The lower hydration energy of the potassium ion enhanced CBZ adsorption on MIL-53(Al), while the higher hydration energy of calcium and magnesium ions reduced the adsorption capacity of CBZ and CIP on MIL-53(Al) and UiO-66(Zr). CBZ interacted with fractionated humic acid better than CIP. High-density carboxylic and aromatic functional groups on humic acid ensured that only humic acid larger than 1KDa was adsorbed by MIL-53(Al). Tryptophan-like and humic acid-like DOM were both detected in real hospital effluent, and their effects on CIP and CBZ adsorption onto MIL-53(Al) were investigated. The presence of tryptophan did not affect CBZ adsorption on MIL-53(Al) (except when coexisting with calcium ions). Conversely, tryptophan interfered with CIP adsorption. The presence of humic acid lower than 1KDa promoted the adsorption of CBZ and CIP by increasing the breathing effect of MIL-53(Al)'s 1D flexible framework. The presence of humic acid with molecular size greater than 1KDa enhanced both CBZ and CIP adsorption via a multilayer adsorption mechanism.

Vacuum ultraviolet irradiation for mitigating dissolved organic nitrogen and formation of haloacetonitriles.

The main objective of this work was to investigate the feasibility of using vacuum ultraviolet (VUV, 185 + 254 nm) and ultraviolet (UV, 254 nm) for the reduction of dissolved organic nitrogen (DON) and haloacetonitrile formation potential (HANFP) of surface water and treated effluent wastewater samples. The results showed that the reduction of dissolved organic carbon (DOC), DON, hydrophobicity (HPO), absorbance at 254 nm (UV254), and fluorescence excitation-emission matrix (FEEM) of both water samples by VUV was higher compared to using UV. The addition of H2O2 remarkably improved the performances of VUV and UV. VUV/H2O2 exhibited the highest removal efficiency for DOC and DON. Even though HANFP increased at the early stage, its concentration decreased (19-72%) at the end of treatment (60 min). Decreases in DON (30-41%) and DOC (51-57%) led to HANFP reduction (53-72%). Moreover, FEEM revealed that substantial reduction in soluble microbial product-like compounds (nitrogen-rich organic) had a strong correlation with HANFP reduction, implying that this group of compounds act as a main precursor of HANs. The VUV/H2O2 system significantly reduced HANFP more than UV/H2O2 and therefore is suitable for controlling HAN precursors and HAN formation in drinking water and reclaimed wastewater.

Selective adsorption mechanisms of pharmaceuticals on benzene-1,4-dicarboxylic acid-based MOFs: Effects of a flexible framework, adsorptive interactions and the DFT study.

The synergetic effects of benzene-1,4-dicarboxylic acid (BDC) linker structure and the metal cluster of MOFs on adsorption mechanisms of carbamazepine, ciprofloxacin and mefenamic acid were investigated in single and mixed solutions. A 1D flexible framework MIL-53(Al), 3D rigid framework UiO-66(Zr) and 3D flexible framework MIL-88B(Fe) were applied as adsorbents. The breathing effect of MIL-53(Al) caused by its flexible structure can enhance intraparticle diffusion for all pharmaceuticals and perform a critical role in excellent adsorption performances. The 3D rigid BDC structure of UiO-66(Zr) caused a steric effect that reflected low or negligible adsorption. Unless concerning accessibility through the internal structure of the MOFs, the binding strengths calculated by the DFT study were in the following order: MIL-88B(Fe) > MIL-53(Al) > UiO-66(Zr). The Fe cluster in MIL-88B(Fe) seems to have the highest affinity for the carboxylic group of pharmaceuticals compared with Al and Zr; however, the lower porosity of MIL-88B(Fe) might limit the adsorption capacity. Moreover, in mixed solutions, the higher acidity of mefenamic acid can enhance competitive performance in interactions with the metal cation cluster of each MOF. Together with the breathing effect, H-bonding and π-π interaction were shown to be the alternative interactions of synergetic adsorption mechanisms.

Solvent-based washing as a treatment alternative for onshore petroleum drill cuttings in Thailand.

In Thailand, onshore drill cuttings (DC) contaminated with total petroleum hydrocarbon (TPH) are currently transported off-site for incineration, causing high transportation cost and potential leakage to the environment. To address the issues, we develop solvent-based washing as a greener alternative for onshore DC remediation, focusing on solvent selection, washing process optimization, and solvent recovery. The results showed that ethyl lactate (EL) was the best green solvent for DC washing, compared to water, ethylene glycol, and ethyl acetate. Based on response surface methodology assisted with central composite design, the maximum TPH removal of 87.1% was achieved from 4 mL g-1 liquid-to-solid ratio, 14 min washing time, and 80 rpm stirring speed, and the TPH removal rate by EL fitted well with the second-order reaction (R2 = 0.9774). Furthermore, the spent EL was successfully recycled by simple and low-energy adsorption using granular activated carbon (GAC). With the sufficient GAC dosage, TPH could be completely removed from the spent EL without impairing the original EL properties. Moreover, the recycled EL exhibited its successful reuse in the subsequent DC washing process. These findings suggest that solvent washing accompanied with solvent recovery by adsorption could be a novel and greener remedial scheme for onshore DC management.

Amino-functionalized mesoporous silica-magnetic graphene oxide nanocomposites as water-dispersible adsorbents for the removal of the oxytetracycline antibiotic from aqueous solutions: adsorption performance, effects of coexisting ions, and natural organic matter.

The amino-functionalized mesoporous silica-magnetic graphene oxide nanocomposite (A-mGO-Si) was synthesized and used for oxytetracycline (OTC) removal from water. Various factors like the effects of initial concentration, contact time, and influence of pH were investigated. Selective adsorption experiments in connection with coexisting ions and dissolved organic matter (DOM) were also investigated. In this study, humic acid (HA) and tannic acid (TA) were representative of both hydrophobic and hydrophilic DOM, respectively. Results indicated that A-mGO-Si had an adsorption ability for OTC that was relatively greater than that of virgin magnetic graphene oxide (mGO), graphene oxide (GO), Fe3O4 particles, and SBA-15 mesoporous silica and also showed a better uptake removal capacity for OTC at low initial concentration in comparison with the other adsorbents. The adsorption behavior of OTC onto A-mGO-Si could be described by the pseudo-second-order kinetic model and the Freundlich isotherm model. The electrostatic interaction has no influence on the OTC absorbed when the OTC is in an aqueous medium in its zwitterion form (3.22 < pH < 7.46). At high pH, the weak π-π EDA interactions and hydrogen bonding may manifest themselves, hence causing a lower adsorption capacity. The main adsorption mechanisms were plausibly activated by H-bonding, and π-π EDA interactions, while the electrostatic interaction (cation-π interaction) might be the minor adsorption mechanism. Addition of individually exogenous ions (Na+, Mg2+, NO-, and CO32-) resulted in a decrease of OTC adsorption due to the emergence of a competitive effect. Considering the presence of HA and TA in mixed solute systems, the DOM was likely to form a stronger interaction system with mGO-Si, thereby resulting in an adsorption level which was more competitive in the process at low aqueous phase concentration of OTC. In contrast to the high aqueous phase, the coexistence of DOM could promote OTC adsorption. The phenomenon may reflect the result that a surface complexation mechanism could achieve in adsorptions.

Adsorption of single and mixed haloacetonitriles on silica-based porous materials: Mechanisms and effects of porous structures.

Adsorption mechanisms and the role of different porous and crystalline structures on the removal of five haloacetonitriles (HANs) over hexagonal mesoporous silica (HMS), titanium substituted mesoporous silica (Ti-HMS), rod-shaped SBA-15 and microporous zeolite NaY were investigated. In addition, the effect of pH on adsorption mechanism and selective adsorption of five HANs individually and in an equimolar mixed solution were evaluated. The results indicated that the intraparticle diffusion rate constants of the mesoporous adsorbents were higher than that of the microporous NaY. In single solute, the order of adsorption preference (highest to lowest) was mono-HANs > di-HANs > tri-HAN. However, in mixed solute, the large molecular weight of the tri-HAN and di-HANs are more easily adsorbed than the smaller molecular weight mono-HANs. Except for SBA-15, the order of adsorption capacities in mixed HANs solute was not different compared to that observed for the single HAN solute, which might be caused by the higher accessibility to the active sites due to larger pore size. The ion-dipole electrostatic interaction was likely to be the main adsorption mechanism, and was favored at high pH values due to the high negative surface charge density of the adsorbent. The molecular structure of the HANs and hydrophilic/hydrophobic nature affected the adsorption capacities and their selective adsorption from mixed solutes.

Photodegradation of haloacetonitriles in water by vacuum ultraviolet irradiation: Mechanisms and intermediate formation.

Photodegradation of haloacetonitriles (HANs), highly carcinogenic nitrogenous disinfection by-products, in water using vacuum ultraviolet (VUV, 185 + 254 nm) in comparison with ultraviolet (UV, only 254 nm) was investigated. Monochloroacetonitrile (MCAN), dichloroacetonitrile (DCAN), trichloroacetonitrile (TCAN), and dibromoacetonitrile (DBAN) were species of HANs studied. The effect of gas purging and intermediate formation under VUV were examined. The results show that the pseudo first order rate constants for the reduction of HANs under VUV were approximately 2-7 times better than UV. The order of degradation efficiency under VUV and UV was MCAN < DCAN < TCAN < DBAN. The degradation efficiencies of individual HANs under VUV were higher than those of mixed HANs, suggesting competitive effects among HANs. Under nitrogen purging, the removal rate constants of mixed HANs was much higher than that of the aerated condition by 34.4, 34.9, 10.1, and 3.8 times for MCAN, DCAN, TCAN, and DBAN, respectively. The major degradation mechanism for HANs was different depending on HANs species. Degradation intermediates of HANs such as 2-chloropropionitrile, 2,2-dimethylpropanenitrile, and fumaronitrile were produced from the substitution, addition, and polymerization reactions. In addition, chlorinated HANs with lower number of chlorine atom including MCAN and DCAN were found as intermediates of DCAN and TCAN degradation, respectively.

Selective adsorption mechanisms of antilipidemic and non-steroidal anti-inflammatory drug residues on functionalized silica-based porous materials in a mixed solute.

The selective adsorption mechanisms of naproxen (NAP), acetaminophen (ACT), and clofibric acid (CFA) on silica-based porous materials were examined by single and mixed-batch adsorption. Effects of the types and densities of surface functional groups on adsorption capacities were determined, including the role of hydrophobic and hydrophilic dissolved organic matters (DOMs). Hexagonal mesoporous silica (HMS), superparamagnetic HMS (HMS-SP) and SBA-15 were functionalized and applied as adsorbents. Compared with powdered activated carbon (PAC), amine-functionalized HMS had a better adsorption capacity for CFA, but PAC possessed a higher adsorption capacity for the other pharmaceuticals than HMS and its two derivatives. In contrast to PAC, the adsorption capacity of the mesoporous silicas varied with the solution pH, being highest at pH 5. Electrostatic interactions and hydrogen bonding were found to be the main mechanisms. Increase in grafted amine group density on silica surfaces can enhance the CFA adsorption capacity. Further, hydrophilic DOM can decrease CFA adsorption capacities on amino-grafted adsorbents by adsorption site competition, while hydrophobic DOM can interfere with CFA adsorption by the interaction between hydrophobic DOM and CFA. Finally, in a competitive adsorption study, the adsorption capacity of hydrophilic adsorbents for acidic pharmaceuticals varied with their pKa values.

Removal of haloacetonitriles in aqueous solution through adsolubilization process by polymerizable surfactant-modified mesoporous silica.

To investigate the adsorption properties and mechanisms of haloacetonitriles (HANs), large-pore SBA-15 mesoporous silica (SBA-CHX) was synthesized using cyclohexane as a swelling agent, and the surface was modified with polymerizable gemini surfactant (PG). The structure and textural properties of the synthesized adsorbents were characterized. PG surfactant coverage on the surface and the degree of polymerization were confirmed with FT-IR analysis. Adsorption experiments were performed under batch conditions to evaluate the influence of the contact time, adsorption isotherms, the effect of the pH solution, and the selective adsorption of five haloacetonitriles (HAN(5)) in individual-solute and mixed-solute solutions and surfactant leaching studies. The results indicated that the hydrophobic HANs were efficiently adsorbed onto PG surfactant-modified SBA-CHX. The selective adsorption mechanisms involved a more complex interplay between the organic partition, surface adsorption (i.e., ion-dipole electrostatic interactions) and hydrophobic interaction that depended upon the adsorbent and adsorbate characteristics. An increased degree of halogen substitution in the HAN molecule significantly affected the adsorption capacity and selectivity by the organic partition. Polymerization of the polymerizable surfactant increased the stability of the adsorbed surfactant on the adsorbent surface.

Adsorption characteristics of haloacetonitriles on functionalized silica-based porous materials in aqueous solution.

The effect of the surface functional group on the removal and mechanism of dichloroacetonitrile (DCAN) adsorption over silica-based porous materials was evaluated in comparison with powdered activated carbon (PAC). Hexagonal mesoporous silicate (HMS) was synthesized and functionalized by three different types of organosilanes (3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane and n-octyldimethysilane). Adsorption kinetics and isotherm models were used to determine the adsorption mechanism. The selective adsorption of five haloacetonitriles (HANs) in the single and mixed solute systems was also studied. The experiments revealed that the surface functional groups of the adsorbents largely affected the DCAN adsorption capacities. 3-Mercaptopropyl-grafted HMS had a high DCAN adsorption capacity compared to PAC. The adsorption mechanism is believed to occur via an ion-dipole electrostatic interaction in which water interference is inevitable at low concentrations of DCAN. In addition, the adsorption of DCAN strongly depended on the pH of the solution as this related to the charge density of the adsorbents. The selective adsorption of the five HANs over PAC was not observed, while the molecular structure of different HANs obviously influenced the adsorption capacity and selectivity over 3-mercaptopropyl-grafted HMS.

Effects of crystalline structures and surface functional groups on the adsorption of haloacetic acids by inorganic materials.

The effects of the crystalline structure and surface functional groups of porous inorganic materials on the adsorption of dichloroacetic acid (DCAA) were evaluated by using hexagonal mesoporous silicates (HMS), two surface functional group (3-aminopropyltriethoxy- and 3-mercaptopropyl-) modified HMSs, faujasite Y zeolite and activated alumina as adsorbents, and compared with powdered activated carbon (PAC). Selective adsorption of HAA(5) group was studied by comparing single and multiple-solute solution, including effect of common electrolytes in tap water. Adsorption capacities were significantly affected by the crystalline structure. Hydrogen bonding is suggested to be the most important attractive force. Decreasing the pH lower than the pH(zpc) increased the DCAA adsorption capacities of these adsorbents due to electrostatic interaction and hydrogen bonding caused by protonation of the hydronium ion. Adsorption capacities of HAA(5) on HMS did not relate to molecular structure of HAA(5). Common electrolytes did not affect the adsorption capacities and selectivity of HMS for HAA5, while they affected those of PAC.

Selective adsorption of nonionic surfactant on hexagonal mesoporous silicates (HMSs) in the presence of ionic dyes.

Selective adsorption of alkylphenol polyethoxylates (APnEOs) from synthetic textile wastewater was investigated using hexagonal mesoporous silicates (HMSs). HMSs are synthetic silicate that have uniform mesopores, large surface areas and uniform surface functional groups. Five different types of HMSs were synthesized by surfactant-templating methods, and three of them were grafted with organic surface functional groups, i.e., n-octyldimethyl-, 3-aminopropyltriethoxy-, and 3-mercaptopropyl-groups. Titanium-substituted HMS was also made in the same way as HMS. Adsorption capacities and selectivities of these HMSs for APnEOs were investigated in batch adsorption experiments either in single-solute APnEO solutions or in mixed solutions with ionic dyes. Triton X-100 was used as a model APnEO and either Basic Yellow 1 or Acid Blue 45 was used as cationic or anionic dyes, respectively. All the HMSs except 3-aminopropyltriethoxy-grafted HMS had higher adsorption capacities of Triton X-100 than powdered activated carbon. HMS and Ti-HMS had the highest BET surface areas and mesopore volumes measured by the nitrogen adsorption method, and thereby the highest adsorption capacities for Triton X-100. Surface charge was the most important attractive force between HMSs and dyes. FT-IR spectra proved that hydrophilic HMSs adsorbed both Basic Yellow 1 and Acid Blue 45 by hydrogen bonding. Acid-base titration experiments revealed that all the HMSs except 3-aminopropyltriethoxy-grafted HMS were negatively charged at neutral pH, whereas PAC and 3-aminopropyltriethoxy-grafted HMS were positively charged. Due to negative surface charge, the anionic dye (Acid Blue 45) was not adsorbed on the four HMSs, which proves high selectivities of these HMSs for Triton X-100 over Acid Blue 45. On the contrary, a small amount of cationic dye (Basic Yellow 1) was adsorbed on all HMSs, but 3-aminopropyltriethoxy-grafted HMS showed the lowest adsorption capacity for Basic Yellow 1 due to positive surface charge. Unlike other silicate adsorbents, no surface solubilization was observed for all HMSs.