[Preparation of Catalyst Cyclodextrin-Fe-TAML to Activate H2O2 and Oxidize Organic Micropollutants in Water].

In order to improve the stability and catalytic activity of Fe-TAML, mono-6-oxy-cyclodextrin bonded Fe-TAML catalyst (CD-Fe-TAML) was prepared by bonding Fe-TAML with cyclodextrin (CD) through chlorosulfonylation reaction, metal chelation reaction, and nucleophilic substitution reaction. The catalytic activity and stability of CD-Fe-TAML and the oxidation degradation efficiencies of 34 organic micropollutants such as antibiotics and pesticides by activation of H2O2in water were studied. Compared with that of Fe-TAML, CD-Fe-TAML at pH 7.0 had a 49-fold and 25-fold increase in the rate of activating H2O2 to produce iron (Ⅴ/Ⅳ)-oxo intermediates and the degradation rate of the substrate, respectively, and its self-oxidation rate was reduced by 70%. The stability of CD-Fe-TAML was 0.7-699 times higher than that of Fe-TAML in the pH range of 3.0-10.0. Specifically, the stability of CD-Fe-TAML was 33-699 times higher than that of Fe-TAML in the pH range of 3.0-7.0. The sulfonic acid group in the molecular structure of CD-Fe-TAML had an electrophilic effect, which could increase the positive charge density of Fe in the active center, accelerate the O-O bond cleavage of H2O2 and the generation of iron(Ⅴ/Ⅳ)-oxo intermediates, improve the catalytic activity of Fe-TAML, and also improve its hydrolysis stability. Meanwhile, the CD group in the molecular structure had the "electron shuttle" effect and inclusion effect. The former could accelerate the electron transfer between the active center Fe-TAML and H2O2 to improve the catalytic activity of Fe-TAML. The latter could inhibit the hydrolysis and self-oxidation of the active center Fe-TAML by inclusion or binding of the hydrolysis sites and oxidation sites, thus improving its stability. The degradation efficiencies of micropollutants by CD-Fe-TAML/H2O2 under weakly acidic and neutral conditions (in the pH range of 5.0-7.0) were 0.4-59 times higher than those of Fe-TAML/H2O2. The degradation efficiencies of CD-Fe-TAML/H2O2 on nine micropollutants with a molar volume less than 0.20 L·mol-1, such as acetamiprid and sulfadiazine, were 0.3-1.1 times higher than that of Fe-TAML/H2O2 at pH 8.0, and there were no significant differences between CD-Fe-TAML/H2O2 and Fe-TAML/H2O2for micropollutants with a molar volume greater than 0.20 L·mol-1. The results of iodide oxidation by CD-Fe-TAML/H2O2 showed that I- was not oxidized to produce iodo-disinfection byproducts (I-DBPs). The degradation of micropollutants by CD-Fe-TAML/H2O2 in the surface water sample was not disturbed by water components. The CD-Fe-TAML/H2O2 system has a potential application in the removal of organic micropollutants from water.

Development of structural equation models to unveil source-sink switches of mid-latitude soils for semi-volatile banned pesticides.

A variety of semi-volatile banned pesticides (SVBPs) are ubiquitous in soils of mid-latitude regions. SVBPs undertake complicated soil-gas exchange processes in mid-latitude regions, challenging the understanding of source or sink roles of soils for the semi-volatile contaminants. Herein, we develop structural equation models (SEMs) to unveil source or sink roles of mid-latitude soils (Liaoning, China) in winter and summer for 12 SVBPs (7 organochlorine and 5 organophosphorus pesticides). The 12 SVBPs exhibit different distribution patterns in soils, dependent of sampling seasons, soil characteristics, topographic/climate conditions of soil sites and chemical properties of compounds. SEM Model I (winter) and Model II (summer) reveal the distribution patterns of SVBPs in soils over season changes, indicating sink-source switches of soils for SVBPS from winter to summer. In winter, soil is a sink of 12 SVBPs in the study area, associated with the inputs of SVBPs in soils by air-particulate partition and dry depositions. However, in summer, soil is mainly a source of the same contaminants, mainly through the volatilization and leaching of SVBPs in soils. The sink-source switches of soils for SVBPs are usually dependent of chemical properties of compounds to higher extents than soil characteristics and topographic/climate conditions of soil sites, though these parameters pose different influences in winter and summer. It has been revealed that soil acts as a sink of SVBPs in winter, associated with the inputs of SVBPs in soils by air-particulate partition and dry depositions, whereas soil acts as a source of SVBPs in summer, mainly through the volatilization and leaching of SVBPs in soils. This finding may provide new insights into the unique distribution patterns of SVBPs in soils in mid-latitude regions.

Insights into site-specific influences of emission sources on accumulation of heavy metal(loid)s in soils by wheat grains.

Excessive accumulation of heavy metal(loid)s in agricultural environment usually originates from anthropogenic activities. Both large diversities of emission sources and complexity of plant accumulation challenge the understanding of the site-specific effects of emission sources on heavy metal(loid)s in wheat grains. Herein, both soil samples and wheat grain samples (n = 80) were collected from the farmland of Jiyuan City, China. Soil and grain burdens of heavy metal(loid)s were determined by inductively coupled plasma mass spectrometry (ICP-MS) and/or X-ray fluorescence spectrometry (XRF). The quotients (Q) were developed to indicate relative impacts of industrial plants and traffic to soil sites. Principal component analysis-absolute principal component scores-multivariate linear regression (PCA-APCS-MLR) analysis was conducted to reveal the source contributions to heavy metal(loid)s in grains, considering Q values, soil, and wheat grain data. Results showed that contributions of main sources and factors drastically varied with soil sites, and usually overlapped to different extents. For grain Cd and grain Pb, natural soil silicate (0.066/0.104 mg/kg) and iron-bearing minerals (- 0.044/ - 0.174 mg/kg) contributed to high extents, while metal smelting activities (0.018/0.019 mg/kg) and agronomic activities (- 0.017/ - 0.019 mg/kg) unexpectedly posed low or moderate contributions. The pH-mediated availability of soil Cd (0.035 mg/kg) and the sand-dust weather (0.028 mg/kg) also made considerable contributions to grain Cd. For grain As, both natural soil iron-bearing (- 0.048 mg/kg) and silicate minerals (- 0.013 mg/kg) made negative contributions. The results benefit to the decision-making of pollution remediation of farmland soils in the regional scales.

Urea/sodium hydroxide pretreatments enhance decomposition of maize straw in soils and sorption of straw residues toward herbicides.

Because of the rigid crystalline structure and recalcitrant components, maize straw returned is slowly decomposed in soils. Straw residues are substantially accumulated in soils and pose detrimental impacts to crop plantation. Here we report the pretreatments of urea and NaOH (USH) to enhance maize straw decomposition in the field. The USH reagents interacted synergistically to destruct straw, mainly through breaking the rigid hydrogen bonding network and chemically hydrolyzing recalcitrant lignin. The synergy was evident for the USH reagents containing 6-8% urea and 0.1-1% NaOH under various temperature conditions (-20 °C to 25 °C). The USH (7%/0.1%) pretreatment resulted in notable enhancement (37%) of straw decomposition in the field within 6 months, superior to current biological-based treatments (6-28%). Moreover, this pretreatment posed no influence on the adsorption of straw residues collected at the early stage of decomposition (27 days) toward five commonly used herbicides. Those straw residues collected on 67 days and later exhibited high adsorption capacity, indicated by 0.5- to 4-folded increases in Kd values. Additionally, the impacts to soil pH and bacterial/fungal community were negligible. The USH pretreatments thus have practical interests in mitigating accumulation of straw residues in straw-returned soils.

Changeable effects of coexisting heavy metals on transfer of cadmium from soils to wheat grains.

Cadmium (Cd) and other heavy metals usually coexist in soils. Effects of coexisting heavy metals on the accumulation and transfer of Cd in field soils by wheat remain poorly understood. Here we revealed changeable effects of coexisting Pb, Zn and Cu on the Cd transfer from soils to wheat grains. Soil burdens of Cd were found to exhibit positive correlations (r = 0.459-0.946) with those of coexisting Pb, Zn and Cu (particularly Pb). Effects of three coexisting metals on to the uptake of Cd by wheat varied in the directions and/or extents with types of metals and transfer processes of Cd. Coexisting Zn inhibited the uptake of Cd by wheat grains to higher extent than Pb and Cu. Soil Zn, along with soil Cd, soil pH and soil Ca, was used to construct the predictive model of grain Cd (R2 = 0.868). External verifications of the model on 572 datasets of large representation performed well. The predictive accuracy was about 54%, 73% and 89% for a factor of 1, 2 and 5 above and below the ideal fit, respectively. This finding has practical interest in risk assessments and remediation measures of Cd-contaminated soil sites in regional scales.

Bioavailability for organic chemical bioaccumulation follows the power law.

Despite the importance of bioavailability for organic chemical bioaccumulation by terrestrial and benthic invertebrates, the principles of bioavailability for organic chemical bioaccumulation remain poorly understood. Here we use large-scale databases with contrasting geographic, compound and organism coverage (from 925 sites, 446 compounds and 184 invertebrate species), and report that bioavailability for organic chemical bioaccumulation follows the power law. It represents that the internal concentration of organic chemicals is the composite power function of the lipid fraction of invertebrates, bulk site concentration of compounds, and organic carbon content of soils/sediments. This law directly links environmental exposures and body burdens of organic chemicals in contaminated sites, and provides a method for enabling case-specific risk assessments of a vast number of organic chemicals and contaminated sites. Our findings may pave the way for translating bioavailability knowledge into risk-oriented regulation of organic chemicals and contaminated sites.

Effects of accumulated straw residues on sorption of pesticides and antibiotics in soils with maize straw return.

Outspread straw return practice leads to accumulation of structurally diverse organic materials in soils, including raw straw and straw residues. This practice provides a supplementary source of organic sorbents for compounds released into soils. However, effects of accumulated straw materials on sorption of compounds in soils remain poorly understood. Here we report that straw materials accumulated in soils display changing chemical structure and properties during decomposition, the majority of which distribute in exponential growth or decay manners with decomposition extents of materials. Sorption of straw materials toward 40 commonly used pesticides and antibiotics takes a compromise of decreasing crystalline index and increasing water absorption capacity of the sorbent materials during decomposition. This tradeoff in sorption leads to case-specific sorption trends of organic compounds in soils with straw return practice, following a composite linear sorption model of mixed soils and straw materials. The predictive model shows that relatively hydrophobic, hydrogen bond acceptor-rich chemicals (about 22.5% of the 40 compounds) display decreasing sorption capacity in organic matter-rich and/or relatively acidic soils with straw return. This finding may contradict the notion that crop straw return usually increases sorption and decreases leaching of compounds in soils.

Facile combinations of thiosulfate and zerovalent iron synergically immobilize cadmium in soils through mild extraction and facilitated immobilization.

Cadmium (Cd) is one of the most toxic substances released in the environment. Cd-contaminated soils usually have a large pool of bioavailable Cd species and lead to excessive Cd accumulation in planted cereal crops. Treatment methods for stable immobilization of Cd in soils are desirable. Here we reported that facile combinations of thiosulfate (STS) and zerovalent iron (ZVI) reinforced Cd immobilization in soils and reduced Cd accumulation in wheat. STS mildly activated Cd in soils through the formation of soluble Cd(S2O3)x complexes, whereas intermediates of STS (e.g., sulfate and sulfides) and ZVI synergically facilitated immobilization of Cd in soils. The synergy was ascribed to the facilitated formation of FeOOH with high Cd-binding affinity and formation of stable sulfate-Cd-FeOOH complexes and poorly available CdSx. STS-ZVI treatments increased residual Cd in soils by 101-123% and decreased Cd accumulation in wheat shoots by 13-68%, depending on chemical compositions and doses of binary reagents. Field applications of STS and ZVI (0.06-0.11 kg/m2) demonstrated 24-39% reductions of grain Cd.

Interrelated effects of soils and compounds on persulfate oxidation of petroleum hydrocarbons in soils.

Persulfate-based chemical oxidation of petroleum hydrocarbons (TPHs) in soils usually varies drastically with soil sites. Complex effects of soil components on persulfate oxidation of TPHs remains poorly understood, impeding the understanding of persulfate oxidation in practical systems. Here we provided empirical evidence for the interrelated effects of natural soils components and target TPHs on persulfate oxidation of TPHs. Inputs of TPHs led to notable alterations of organic matter, minerals and pH of soils, which in turn influenced distributions and availability of TPHs in soils. These soil/TPH properties and oxidant dose constituted five interrelated terms that were used to develop a predictive model of persulfate oxidation of TPHs. Such interrelation accounted for ilmenite-base coupling activation of persulfate oxidation, Fe/Mn mineral activation of persulfate oxidation, chemical oxidant demand of soils, mass transfer-reactivity limiting of TPHs, and applicable parameters of persulfate oxidation, respectively. The interrelation-based model of persulfate oxidation of TPHs displayed high predictive accuracy of 43% for a factor of 0.3 above and below the ideal fit, despite large differences in contaminated sites and applicable parameters. This finding may have practical interests in the optimization of persulfate oxidation.

Predicting plant cuticle-water partition coefficients for organic pollutants using pp-LFER model.

Predicting plant cuticle-water partition coefficients (Kcw) and understanding the partition mechanisms are crucial to assess environmental fate and risk of organic pollutants. Up to now, experimental Kcw values are determined for only hundreds of compounds because of high experimental cost. For this reason, computational models, which can predict Kcw values based on chemical structures, are promising approaches to evaluate new compounds. In this study, a large dataset consisting of 279 logKcw values for 125 unique compounds were collected and curated. A poly-parameter linear free energy relationship (pp-LFER) model was developed with stepwise multiple linear regression based on this dataset. The resulted pp-LFER model has good predictability and robustness as indicated by determination coefficient (R2adj,tra) of 0.93, bootstrapping coefficient (Q2BOOT) of 0.92, external validation coefficient (Q2ext) of 0.94 and root mean square error of 0.52 log units. Contribution analysis of different interactions indicated that dispersion and hydrophobic interactions have the highest positive contribution (56%) to increase the partition of pollutants onto plant cuticles. In addition, for organic pollutions containing benzene ring (13-31%), double bond (9-17%) or nitrogen-containing heterocycles (9-17%), π/n-electron pairs interactions exhibit obvious positive contributions to logKcw. In conclusion, the proposed pp-LFER model is beneficial for predicting logKcw of potential organic pollutants directly from their molecular structures.

Development of a Passive Sampling Technique for Measuring Pesticides in Waters and Soils.

It is essential to monitor pesticides in the environment to help ensure water and soil quality. The diffusive gradients in thin-films (DGT) technique can measure quantitative in situ labile (available) concentrations of chemicals in water, soil, and sediments. This study describes the systematic development of the DGT technique for nine current pesticides, selected to be representative of different classes with a wide range of properties, with two types of resins (HLB (hydrophilic-lipophilic-balanced) and XAD 18) as binding layer materials. The masses of pesticides accumulated by DGT devices were proportional to the deployment time and in inverse proportion to the thickness of the diffusive layer, in line with DGT theoretical predictions. DGT with both resin gels were tested in the laboratory for the effects of typical environmental factors on the DGT measurements. DGT performance was independent of the following: pH in the range of 4.7-8.2; dissolved organic matter concentrations <20 mg L-1; and ionic strength from 0.01 to 0.25 M, although it was slightly affected at 0.5 M in some cases. This confirms DGT as a sampler suitable for controlled studies of environmental processes affecting pesticides. Field applications of DGT to measure pesticides in situ in waters and controlled laboratory measurements on five different soils (prepared at fixed soil/water ratios) demonstrated DGT is a suitable tool for environmental monitoring in waters and for investigating chemical processes in soils.

DOM from mariculture ponds exhibits higher reactivity on photodegradation of sulfonamide antibiotics than from offshore seawaters.

Mariculture activities and river inputs lead to coastal seawaters with DOM levels that are comparable to or even higher than those in terrestrial water bodies. However, effects of seawater DOM, and especially of DOM occurring in areas impacted by mariculture, on photodegradation of organic micropollutants, are largely unknown. In this study, simulated sunlight irradiation experiments were performed to probe the effects of DOM extracted from mariculture impacted seawaters and from offshore areas, on photodegradation of three sulfonamide antibiotics (SAs). Results show that the SAs are transformed mainly by indirect photodegradation induced by triplet excited DOM (3DOM*). Compared with DOM from the more pristine coastal waters, the DOM from mariculture impacted areas undergoes less photobleaching, contains higher percentage of humic-like materials and higher proportions of aromatic and carbonyl structures. Thus, the DOM from mariculture areas exhibits higher rates of light absorption, higher formation quantum yields of 3DOM*, higher 3DOM* steady-state concentrations and higher reactivity on photodegradation of the SAs. Photochemistry of the seawater DOM is different from that reported for freshwater lake DOM. This study highlights the importance of probing the effects of DOM from coastal seawaters on photodegradation of organic micropollutants since coastal seawaters are sinks of many aquatic pollutants.

Bioaccumulation and tissue distribution of antibiotics in wild marine fish from Laizhou Bay, North China.

Information about bioaccumulation and tissue distribution of antibiotics in wild marine fish is still limited. In the present study, tissue levels, bioaccumulation and distribution patterns of 9 sulfonamide (SA), trimethoprim (TMP), 5 fluoroquinolone (FQ), and 4 macrolide (ML) antibiotics were investigated in gill, muscle, kidney, and liver tissues of seven wild fish species collected from Laizhou Bay, North China in 2016. All the 19 antibiotics were detected in these fish tissues with the total concentrations ranging from 22ng/g dry weight (dw) to 500ng/g dw. The mean values of logarithm bioaccumulation factors (BAFs) in the gills, muscles, kidneys, and livers ranged from 2.2 to 4.8, 1.9 to 4.0, 2.5 to 4.9, and 2.5 to 5.4, respectively. Log BAFs of antibiotics in these tissues significantly increased (r=0.61-0.77, p<0.001) with their logarithm values of liposome-water distribution coefficient (Dlipw) except in the muscles, suggesting that Dlipw can well assess the bioaccumulation potentials of antibiotics in phospholipid-rich tissues. In general, the SAs, TMP, and FQs were primarily accumulated in the muscles and the MLs were primarily in the livers, which may be related to their toxicokinetic processes of these marine fish. The present study for the first time reported the tissue distribution patterns of antibiotics in wild marine fish.

Different binding mechanisms of neutral and anionic poly-/perfluorinated chemicals to human transthyretin revealed by In silico models.

Chemical forms-dependent binding interactions between phenolic compounds and human transthyretin (hTTR) have been elaborated previously. However, it is not known whether the binding interactions between ionizable halogenated alphatic compounds and hTTR also have the same manner. In this study, poly-/perfluorinated chemicals (PFCs) were selected as model compounds and molecular dynamic simulation was performed to investigate the binding mechanisms between PFCs and hTTR. Results show the binding interactions between the halogenated aliphatic compounds and hTTR are related to the chemical forms. The ionized groups of PFCs can form electrostatic interactions with the -NH+3 groups of Lys 15 residues in hTTR and form hydrogen bonds with the residues of hTTR. By analyzing the molecular orbital energies of PFCs, we also found that the anionic groups (nucleophile) in PFCs could form electron donor - acceptor interactions with the -NH+3 groups (electrophile) in Lys 15. The aforementioned orientational interactions make the ionized groups of the PFCs point toward the entry port of the binding site. The roles of fluorine atoms in the binding interactions were also explored. The fluorine atoms can influence the binding interactions via inductive effects. Appropriate molecular descriptors were selected to characterize these interactions, and two quantitative structure-activity relationship models were developed.

Antibiotic Pollution in Marine Food Webs in Laizhou Bay, North China: Trophodynamics and Human Exposure Implication.

Little information is available about the bioaccumulation and biomagnification of antibiotics in marine food webs. Here, we investigate the levels and trophic transfer of 9 sulfonamide (SA), 5 fluoroquinolone (FQ), and 4 macrolide (ML) antibiotics, as well as trimethoprim in nine invertebrate and ten fish species collected from a marine food web in Laizhou Bay, North China in 2014 and 2015. All the antibiotics were detected in the marine organisms, with SAs and FQs being the most abundant antibiotics. Benthic fish accumulated more SAs than invertebrates and pelagic fish, while invertebrates exhibited higher FQ levels than fish. Generally, SAs and trimethoprim biomagnified in the food web, while the FQs and MLs were biodiluted. Trophic magnification factors (TMF) were 1.2-3.9 for SAs and trimethoprim, 0.3-1.0 for FQs and MLs. Limited biotransformation and relatively high assimilation efficiencies are the likely reasons for the biomagnification of SAs. The pH dependent distribution coefficients (log D) but not the lipophilicity (log KOW) of SAs and FQs had a significant correlation (r = 0.73; p < 0.05) with their TMFs. Although the calculated estimated daily intakes (EDI) for antibiotics suggest that consumption of seafood from Laizhou Bay is not associated with significant human health risks, this study provides important insights into the guidance of risk management of antibiotics.

Recyclable Capture and Destruction of Aqueous Micropollutants Using the Molecule-Specific Cavity of Cyclodextrin Polymer Coupled with KMnO4 Oxidation.

The removal of aqueous micropollutants remains challenging because of the interference of natural water constituents that are typically 3-9 orders of magnitude more concentrated. Cyclodextrins, which feature molecular recognition and are widely applied in separation and catalysis, are promising materials in the development of pollutant treatment technologies. Here, we described the facile integration of cyclodextrin polymer (CDP) adsorption and KMnO4 oxidation for recyclable capture and destruction of aqueous micropollutants (i.e., antibiotics and TBBPA). CDP exhibited adsorption efficiencies of 0.81-88% and 0.81-94% toward 14 pollutants at 50.0 ng/L and 50.0 µg/L, respectively, at a solid-to-liquid ratio of 1:1250. The presence of simulated or natural water constituents (e.g., Mg(2+), Ca(2+), DOC, and a combination thereof) did not decrease the adsorption potential of CDP toward these pollutants because the pollutants, based on molecular specificity, were entrapped in the CD cavity. Subsequent KMnO4 oxidation completely degraded the retained pollutants, demonstrating that the pollutants could be broken down in the cavity. Pristine CDP was rearranged into the structurally loose composites that featured a porous CDP architecture with uniform embedment of δ-MnO2 nanoparticles and different adsorption efficiencies. δ-MnO2 loading was a linear function of the number of times the integrated procedure was repeated, underlying the accurate control of CDP recycling. Thus, this approach may represent a new method for the removal of aqueous micropollutants.

Probing the stereochemistry of successive sulfoxidation of the insecticide fenamiphos in soils.

Successive sulfoxidation is widely recognized as a general characteristic of the metabolism of chiral or prochiral thioethers, producing sulfoxides, and sulfones. However, information related to the stereochemistry of this process in soils is rare. In this study, the biotic transformation of the insecticide fenamiphos (a model thioether) was followed over two months in three soils, through separate incubations with fenamiphos parent, the sulfoxide intermediate (FSO), the sulfone intermediate (FSO2), and their respective stereoisomers. The results showed that the successive sulfoxidation involved oxidation of fenamiphos to FSO and subsequently to FSO2 as well as diastereomerization/enantiomerization of FSO, all of which were primarily biotic and stereoselective. The concomitant hydrolysis of fenamiphos, FSO, and FSO2 to phenols that occurred at lower rates was biotically favorable, but not stereoselective. The stereochemistry of this successive sulfoxidation transferred principally through two parallel systems, R(+)-fenamiphos → SRPR(+)-/SSPR(-)-FSO → R(+)-FSO2 and S(-)-fenamiphos → SRPS(+)-/SSPS(-)-FSO → S(-)-FSO2, between which unidirectional intersystem crossing occurred at FSO via isomeric conversions and created a system of S(-)-fenamiphos → SRPR(+)-/SSPR(-)-FSO → R(+)-FSO2. This pattern accounts for the enrichment of the intermediates SSPR(-)-/SSPS(-)-FSO and R(+)-FSO2 that are toxicologically close to the highly toxic S(-)-fenamiphos, associated with soil application of fenamiphos. Selective formation/depletion of these intermediate stereoisomers leads to dramatic variations in the ecotoxicological effects of the thioether insecticide.

Molecular insights into the pH-dependent adsorption and removal of ionizable antibiotic oxytetracycline by adsorbent cyclodextrin polymers.

Effects of pH on adsorption and removal efficiency of ionizable organic compounds (IOCs) by environmental adsorbents are an area of debate, because of its dual mediation towards adsorbents and adsorbate. Here, we probe the pH-dependent adsorption of ionizable antibiotic oxytetracycline (comprising OTCH2 (+), OTCH(±), OTC(-), and OTC(2-)) onto cyclodextrin polymers (CDPs) with the nature of molecular recognition and pH inertness. OTCH(±) commonly has high adsorption affinity, OTC(-) exhibits moderate affinity, and the other two species have negligible affinity. These species are evidenced to selectively interact with structural units (e.g., CD cavity, pore channel, and network) of the polymers and thus immobilized onto the adsorbents to different extents. The differences in adsorption affinity and mechanisms of the species account for the pH-dependent adsorption of OTC. The mathematical equations are derived from the multiple linear regression (MLR) analysis of quantitatively relating adsorption affinity of OTC at varying pH to adsorbent properties. A combination of the MLR analysis for OTC and molecular recognition of adsorption of the species illustrates the nature of the pH-dependent adsorption of OTC. Based on this finding, γ-HP-CDP is chosen to adsorb and remove OTC at pH 5.0 and 7.0, showing high removal efficiency and strong resistance to the interference of coexisting components.

Evaluating the interactions of organic compounds with multi-walled carbon nanotubes by self-packed HPLC column and linear solvation energy relationship.

Understanding the interactions between organic pollutants and carbon nanotubes (CNTs) is critical for fate assessment of both CNTs and organic pollutants. In this study, the chromatographic approach was introduced based on CNTs as stationary phase for the evaluation of such interactions. The pristine multi-walled carbon nanotubes (MWCNTs) were packed into columns of high-pressure liquid chromatography (HPLC) and the retention factors (k') were determined to characterize the adsorption affinity of organic compounds onto MWCNTs. Nine compounds were tested. The results showed that their lnk' values followed the order: benzene < toluene < phenol < chlorobenzene < bromobenzene < aniline < sulfamethoxazole < sulfadiazine ≈ sulfadimidine. The linear solvation energy relationship (LSER) theory was adopted to correlate lnk' with the molecular solvatochromic parameters. We found that lnk' of the studied compounds correlate positively with molecular polarizability (E) significantly, suggesting that the π-/n-electrons-dependent polarizable interactions play a major role for the adsorption. Moreover, the thermodynamic parameters calculated from van't Hoff equations revealed that the interactions between the compounds and MWCNTs were spontaneous and exothermic processes.

Mathematical model for cyclodextrin alteration of bioavailability of organic pollutants.

While many cyclodextrin-based applications have been developed to assess or enhance bioavailability of organic pollutants, the choice of cyclodextrin (CD) is largely empirical, with little consideration of pollutant diversity and environmental matrix effects. This study aimed at developing a mathematical model for quantifying CD alteration of bioavailability of organic pollutants. Cyclodextrin appears to have multiple effects, together contributing to its bioavailability-enhancing property. Cyclodextrin is adsorbed onto the adsorbent matrix to different extents. The adsorbed CD is capable of sequestrating organic pollutants, highlighting the role of a pseudophase similar to solid environmental matrix. Aqueous CD can reduce adsorption of organic pollutants via inclusion complexation. The two effects cancel each other to a certain degree, which determines the levels of organic pollutants dissolved (comprising freely dissolved and CD-included forms). Additionally, the CD-included form is nearly identical in biological activity to the free form. A mathematical model of one variable (i.e., CD concentration) was derived to quantify effects of CD on the bioavailability of organic pollutants. Model analysis indicates that alteration of bioavailability of organic pollutants by CD depends on both CD (type and level) and environmental matrix. The selection of CD type and amendment level for a given application may be predicted by the model.