Solvophobic approach for predicting sorption of hydrophobic organic chemicals on synthetic sorbents and soils

The application of a solvophobic approach for predicting the sorption of hydrophobic organic compounds (HOC) was evaluated with data collected using synthetic sorbents and soils. The experimental data consisted of batch equilibrium sorption coefficients (K_D), as well as soil-TLC and reversed-phase liquid chromatographic (RPLC) retention factors (κ′). All data were collected using aqueous solutions and binary or ternary solvent mixtures of water, methanol, acetone, and acetonitrile. As predicted by the theory, the chromatographic retention factors and sorption coefficients for HOC decreased log-linearly with increasing fraction of organic cosolvent in binary solvents. Model parameters estimated from the binary solvent data could be used to predict sorption (or retention) from ternary solvents. Reasonable agreement was found between model parameters reported in the literature and those estimated using the data from batch sorption, soil-TLC, and RPLC studies.     

Adsorption of phenolic compounds from aqueous solutions by a water-compatible hypercrosslinked polymeric adsorbent

A water-compatible hypercrosslinked polymeric adsorbent (NJ-8) for adsorbing and removing phenolic compounds from their aqueous solutions was prepared. This product can be used directly without a wetting process. Its adsorption property toward four phenolic compounds, phenol, p-cresol, p-chlorophenol, and p-nitrophenol was tested using the commercial Amberlite XAD-4 as a reference. The capacities of equilibrium adsorption for all four phenolic compounds on the NJ-8 from their aqueous solutions are around two times as high as that of Amberlite XAD4 within the temperature range 283-323 K, which may contribute to their micropore structure and the partial polarity on the network. Freundlich isotherm equations, as well as relative adsorption capacities and isosteric adsorption enthalpies for the four phenolic compounds, indicate that the adsorption of phenolic compounds on the NJ-8 resin is a physical adsorption process. Mini-column adsorption studies for phenol on Amberlite XAD4 and NJ-8 resins show that the breakthrough adsorption capacities are 0.54 and 0.99 mmol/ml, and the total capacities are 0.62 and 1.37 mmol/ml, while no extra acetone was needed to remove the adsorbed phenol from NJ-8 as from Amberlite XAD4.     

Selective removal of some polyhydric phenols from aqueous solution by ferric antimonate

Ferric antimonate, a cation-exchanger, has been investigated as an adsorbent for the removal of phenol and polyhydric phenols from aqueous solution. It has been found that ferric antimonate in H+ form selectively adsorbs polyhydric phenols having hydroxyl groups on adjacent positions. While phenol, resorcinol, and quinol did not show any appreciable adsorption, catechol, pyrogallol, and gallic acid having hydroxyl groups on adjacent positions exhibited considerable adsorption on ferric antimonate. Batch equilibrium experiments were carried out to study the effect of contact time, initial concentration of phenolic compounds, and temperature on the adsorption of phenolic compounds on ferric antimonate. The equilibrium time was found to be 1.5 hours for gallic acid and pyrogallol and 2 hours for catechol and salicylic acid. The adsorption data of the phenols at temperatures of 30 degrees, 40 degrees, and 50 degrees C have been described by Langmuir and Freundlich isotherm models. The best fit was obtained with the Langmuir model in the whole range of concentrations studied at all temperatures, indicating a monolayer adsorption onto a homogeneous adsorption surface. On the basis of the Langmuir isotherm, the maximum adsorption capacity of ferric antimonate for gallic acid, pyrogallol, catechol, and salicylic acid was found to be 3.915, 3.734, 2.397, and 2.758 mg/g, respectively at 30 degrees C. The maximum sorption capacity of ferric antimonate for the phenolic compounds studied is in the following order: gallic acid > pyrogallol > salicylic acid > catechol. The adsorption of phenolic compounds was found to decrease with an increase in temperature. Thermodynamic parameters like free energy, enthalpy, and entropy changes were calculated and discussed. The adsorption of polyhydric phenols on ferric antimonate is exothermic and spontaneous in nature.     

Competitive biosorption of lead, cadmium, copper, and arsenic ions using algae

The present study aims to evaluate the competitive biosorption of lead, cadmium, copper, and arsenic ions by using native algae. A series of experiments were carried out in a batch reactor to obtain equilibrium data for adsorption of single, binary, ternary, and quaternary metal solutions. The biosorption of these metals is based on ion exchange mechanism accompanied by the release of light metals such as calcium, magnesium, and sodium. Experimental parameters such as pH, initial metal concentrations, and temperature were studied. The optimum pH found for removal were 5 for Cd²⁺ and As³⁺ and 3 and 4 for Pb²⁺ and Cu²⁺, respectively. Fourier transformation infrared spectroscopy analysis was used to find the effects of functional groups of algae in biosorption process. The results showed that Pb²⁺ made a greater change in the functional groups of algal biomass due to high affinity to this metal. An ion exchange model was found suitable for describing the biosorption process. The affinity constants sequence calculated for single system was K _Pb > K _Cu > K _Cd > K _As; these values reduced in binary, ternary, and quaternary systems. In addition, the experimental data showed that the biosorption of the four metals fitted well the pseudo-second-order kinetics model.     

Occurrence, distribution, and sources of six phenolic endocrine disrupting chemicals in the 22 river estuaries around Dianchi Lake in China

The objectives of this study are to track the occurrence, distribution, and sources of phenolic endocrine disrupting compounds (EDCs) in the 22 rivers around Dianchi Lake in China, to estimate the input and output amounts of phenolic EDCs in the water system, and to provide more comprehensive fundamental data for risk assessment and contamination control of phenolic EDCs in aquatic environment. Six phenolic EDCs were systematically evaluated in water and surface sediment in the estuaries of those rivers. The water and sediment samples were preconcentrated by solid-phase extraction system and microwave-assisted extraction system, respectively. Phenolic EDCs were analyzed by GC-MS (Thermo Fisher Scientific, USA) after derivatization. Phenolic EDCs were found ubiquitously in the aquatic environment. The total concentrations ranged from 248 to 4,650 ng/L in water, and 113 to 3,576 ng/g dry weight in surface sediment. The residue amount of phenolic EDCs in Dianchi Lake was 258 kg/a. Concentrations of the phenolic EDCs in the Lake decreased with increase in distance to the estuaries of those rivers which run through urban and industrial areas. The rivers seriously contaminated by phenolic EDCs were Xin River, Yunliang River, Chuanfang River, Cailian River, Jinjia River, Zhengda River, and Daqing River which run through the old area of Kunming City. Satisfying correlations were observed between the concentrations of the target compounds in water and in surface sediment. NP1EO, NP2EO, and BPA were identified as the three predominant phenolic EDCs. There were significant correlations between phenolic EDCs and many basic water quality parameters. Urban and industrial areas are the major contributors for phenolic EDCs, especially in Kunming City. Compositional profiles of phenolic EDCs in surface sediment were similar to those in river water. The concentrations of phenolic EDCs in the rivers located in the northwest part of the valley were very high, and posed a potential risk to aquatic organisms and even human. The concentrations of NP2EO, NP1EO, and BPA were at moderate levels of other areas. The basic water quality parameters (TOC, TN, DO, and pH) play important roles on the distribution, fate, and behavior of phenolic EDCs in the valley.     

Identification of organic compounds in municipal landfill leachates

Forty-five organic compounds have been identified in leachates from a Swedish municipal landfill. The samples were taken from the interior of the landfill to minimize alterations caused by contact with the surroundings and were identified and quantified by gas chromatography combined with mass spectrometry. Two analytical procedures were used, one for priority pollutants, the other for a wider range of phenolic and neutral compounds and acids. Analyses of the leachates for water quality parameters indicated that the part of the landfill which was sampled had reached an anaerobic stage in which methane was being produced. Possible origins for most of the compounds identified have been suggested.     

Computer-based QSARs for predicting mixture toxicity of benzene and its derivatives

During the past decades, the Quantitative structure-activity relationships (QSARs) have been proven to be reliable tools when little or no empirical data are available in medicinal chemistry, biochemistry, toxicology, and environmental sciences. However, only few studies that quantitatively predict mixtures toxicity have been reported. In this study, the QASR models for the binary mixtures toxicity of 12 benzene and its derivatives, including eight non-polar-narcotic compounds and four polar narcotic compounds were developed, without reference to exact toxicity mechanisms of single compounds. All parameters for the QSAR studies were defined on the basis of quantum mechanical calculations and these parameters were selected by the stepwise procedure. The results of this study provided a simple means of predicting the binary mixtures toxicity from the chemical structure.     

Sorption equilibria of metal ions on bone char

The ability of bone char to adsorb three metal ions, namely, copper(II), zinc(II) and cadmium(II) ions from wastewater has been studied. Three single-component equilibrium systems and three binary equilibrium systems have been measured experimentally. The three single-component equilibrium data were analyzed using the Langmuir and the Sips equilibrium isotherm equations. The Sips isotherm gave a better fit of the experimental data than the Langmuir isotherm based on the sum of squares errors (SSE) analysis. The Cu-Zn, Cu-Cd and Cd-Zn binary equilibrium experimental data were examined by incorporating the Langmuir and the Sips isotherm equations into the ideal adsorbed solution theory (IAST). The solution methods and the predicted results for the three binary systems at different metal ion compositions have been evaluated. In addition, the application of the IAST to the model prediction for the fixed bed system is presented.     

Toxicity of mixtures of perfluorooctane sulphonic acid with chlorinated chemicals and lipid regulators

The toxicological interaction of perfluorooctane sulphonic acid (PFOS) with the chlorinated pollutants triclosan and 2,4,6-trichlorophenol and the lipid regulators gemfibrozil and bezafibrate was evaluated using the combination index-isobologram equation. The endpoint for bioassays was the growth rate inhibition of the green alga Pseudokirchneriella subcapitata. The results showed that most of the binary combinations assayed exhibited antagonism at all effect levels. The addition of a third component induced a less antagonistic or even synergistic behaviour. This was particularly marked for the ternary mixture of triclosan and 2,4,6-trichlorophenol with PFOS, for which synergism was very strong at all effect levels, with a combination index as low as 0.034 ± 0.002 at EC₅₀ for the mixture. The results obtained indicate that the evaluation of mixture toxicity from single component data using the concentration addition approach could severely underestimate combined toxicity.     

Partial solubility parameters of chlorobenzene and chlorophenol compounds at equilibrium distribution in two immiscible phases

Partial solubility parameters of chlorobenzene and chlorophenol compounds at equilibrium distribution in two immiscible phases such as soil-water system were studied. An integral distribution equilibrium equation is derived from the concept of partial solubility parameters and Flory-Hungins equation. Twelve chlorobenzenes and nineteen chlorophenols were employed in this study and their partial solubility parameters including dispersion( (δ_d),and polar van der Waals (δ_p), as well as their electron acceptor and donor solubility parameters (δ_a and δ_b) were calculated.Hildebrand's solubility parameter(δ) of the compounds was also obtained by using boiling point and formula.HPLC was performed by octadecyl-bonded phase as the stationary phase with methanol or acetonitrile as the mobile phase to determine the capacity factor k′ of all compounds for the calculation of δ_a and δ_b.     

Equilibrium studies for the sorption of lead from effluents using chitosan

The sorption of lead ions from aqueous solution onto chitosan has been studied. Equilibrium studies have been carried out to determine the capacity of chitosan for lead ions. The effects of solution pH and chitosan particle size on the sorption capacity have been studied.The experimental data were analyzed using three equilibrium isotherm correlations, namely, Langmuir, Freundlich and Redlich-Peterson equations. The linear correlation coefficients were determined for each isotherm and the Freundlich provided the best fit. In addition, error functions have been used to determine the alternative single component equilibrium isotherm parameters by non-linear regression due to the inherent bias in using the correlation coefficient from the linearization. This technique enables the "best fit" isotherm parameters to be used in the equilibrium equations for the sorption of lead ions on chitosan within the limits and assumptions of the various error analysis methods.     

Characteristics of photocatalytic oxidation of toluene, benzene, and their mixture

The investigation of the photocatalytic oxidation (PCO) of multicomponent volatile organic compounds (VOCs) is very important to the application of PCO technology, because there is seldom a single VOC component in indoor air. In this paper, the characteristics of binary indoor VOCs, toluene and benzene, were experimentally studied using a mass transfer based method that we developed. The concentration ranges for toluene and benzene were 4.48-27.4 mg/m3 and 1.82-4.08 mg/m3, respectively. We found the following: (1) the PCO of each individual contaminant studied obeys the unimolecular form of the Langmuir-Hinshelwood (L-H) rate form; (2) the PCO of the binary contaminants follow the competitive adsorption L-H rate form; (3) the reaction-coefficient for PCO of individual contaminants differs from that in the competitive adsorption L-H rate form; and (4) the component impact factor of A to B, put forward in this paper, is a useful parameter describing the influence of A on the reaction coefficient of B, and it was found that the impact factor of toluene (a chemically active component) on benzene (a chemically stable component) is high, and the impact factor of benzene on toluene is low.     

A comparison of mixture toxicity assessment: examining the chronic toxicity of atrazine, permethrin and chlorothalonil in mixtures to Ceriodaphnia cf. dubia

Pesticides predominantly occur in aquatic ecosystems as mixtures of varying complexity, yet relatively few studies have examined the toxicity of pesticide mixtures. Atrazine, chlorothalonil and permethrin are widely used pesticides that have different modes of action. This study examined the chronic toxicities (7-d reproductive impairment) of these pesticides in binary and ternary mixtures to the freshwater cladoceran Ceriodaphnia cf. dubia. The toxicity of the mixtures was compared to that predicted by the independent action (IA) model for mixtures, as this is the most appropriate model for chemicals with different modes of action. Following this they were compared to the toxicity predicted by the concentration addition (CA) model for mixtures. According to the IA model, the toxicity of the chlorothalonil plus atrazine mixture conformed to antagonism, while that of chlorothalonil and permethrin conformed to synergism. The toxicity of the atrazine and permethrin mixture as well as the ternary mixture conformed to IA implying there was either no interaction between the components of these mixtures and/or in the case of the ternary mixture the interactions cancelled each other out to result in IA. The synergistic and antagonistic mixtures deviated from IA by factors greater than 3 and less than 2.5, respectively. When the toxicity of the mixtures was compared to the predictions of the CA model, the binary mixture of chlorothalonil plus atrazine, permethrin plus atrazine and the ternary mixture all conformed to antagonism, while the binary mixture of chlorothalonil plus permethrin conformed to CA. Using the CA model provided estimates of mixture toxicity that did not markedly underestimate the measured toxicity, unlike the IA model, and therefore the CA model is the most suitable to use in ecological risk assessments of these pesticides.     

Photo-Fenton treatment of water containing natural phenolic pollutants

Phenolic compounds are known to be present in high concentrations in various types of agro-industrial wastes. As they are highly biorecalcitrant, the possibility of treatment by advanced oxidation processes should be investigated. In this work, six model phenolic compounds (vanillin, protocatechuic acid, syringic acid, p-coumaric acid, gallic acid and L-tyrosine) were chosen for a demonstration of degradation by photo-Fenton reaction, under artificial light in laboratory experiments in Vienna and under sunlight in pilot-plant experiments at the Plataforma Solar de Almería in Spain. All compounds were completely mineralised. No non-degradable intermediates were produced, either in experiments with single substances or in a more complex matrix of a mixture of phenolic compounds. The expected selectivity of the photo-Fenton reaction for aromatic compounds was proven by comparison of the decrease in total organic carbon with the removal of total phenolic content.     

高级氧化技术在含酚废水处理中的应用

合理高效地处理含酚废水是工业废水处理的主要任务之一。重点介绍了高级氧化技术 ,如超声波氧化、超临界水氧化、湿式氧化和光催化氧化等在含酚废水处理中的研究近况和应用前景 ,探讨了各种技术的应用和发展趋势     

Kinetic model for phenolic compound oxidation by Fenton's reagent

A kinetic model is developed for the oxidation of phenolic compounds by Fenton's reagent. In the first stage a rigorous kinetic model is applied to calculate the different kinetic rate constants for the oxidation process of p-hydroxybenzoic acid. In a second phase a competitive method is applied to calculate these kinetic constants for another 10 phenolic compounds present in agroindustrial and pulp paper wastewaters. These 10 phenolic compounds were: beta-resorcylic acid, 3-(4-hydroxyphenyl)-propionic acid, ferulic acid, protocatechuic acid, caffeic acid, p-coumaric acid, vanillic acid, syringic acid, veratric acid and 3,4,5-trimethoxybenzoic acid.     

Influence of fungicide residues and in vitro gastrointestinal digestion on total antioxidant capacity and phenolic fraction of Graciano and Tempranillo red wines

Abstract

The effect of fenhexamid, mepanipyrim and cyazofamid fungicides on in vitro bioavailability of antioxidant activity and phenolic compounds of Tempranillo and Graciano red wine was studied by simulating the digestive process by dialysis in semipermeable membranes. Determination of antioxidant activity was through reaction with the DPPH ? radical and the measurement of phenolic compounds was made with liquid chromatography with diode detector (HPLC-DAD). Fenhexamid, mepanipyrim and cyazofamid reduce the total polyphenol content in both wines. During dialysis there was a large loss of total polyphenols (80–90%) and of antioxidant activity (> 90%). The bioavailability of the phenolic compounds is lower than that for non-treated wines and the highest dialization percentages were found for stilbenes > 50%. While for the remaining phenolic fraction the order is the following hydroxycinnamic derivatives?>?anthocyanins?>?flavonols.