Modified Halloysite as an Adsorbent for the Removal of Cu(II) Ions and Reactive Red 120 Dye from Aqueous Solutions.

The adsorption of copper ions and Reactive Red 120 azo dye (RR-120) as models of water pollutants on unmodified halloysite (H-NM), as well as halloysites modified with sulfuric acid (H-SA) and (3-aminopropyl)triethoxysilane (H-APTES), was investigated. The results showed that adsorption of both the adsorbates was pH-dependent and increased with the increase in halloysite dosage. The adsorption kinetics were evaluated and the results demonstrated that the adsorption followed the pseudo-second-order model. The adsorption isotherms of Cu(II) ions and RR-120 dye on the halloysites were described satisfactorily by the Langmuir model. The maximum adsorption capacities for the Cu(II) ions were 0.169, 0.236, and 0.507 mmol/g, respectively, for H-NM, H-SA, and H-APTES indicating that the NH2-functionalization rather than the surface area of the adsorbents was responsible for the enhanced adsorption. The adsorption capacities for RR-120 dye were found to be 9.64 µmol/g for H-NM, 75.76 µmol/g for H-SA, and 29.33 µmol/g for H-APTES. The results demonstrated that APTES-functionalization and sulfuric acid activation are promising modifications, and both modified halloysites have good application potential for heavy metals as well as for azo dye removal.

Adsorption of Phenoxyacetic Herbicides from Water on Carbonaceous and Non-Carbonaceous Adsorbents.

The increasing consumption of phenoxyacetic acid-derived herbicides is becoming a major public health and environmental concern, posing a serious challenge to existing conventional water treatment systems. Among the various physicochemical and biological purification processes, adsorption is considered one of the most efficient and popular techniques due to its high removal efficiency, ease of operation, and cost effectiveness. This review article provides extensive literature information on the adsorption of phenoxyacetic herbicides by various adsorbents. The purpose of this article is to organize the scattered information on the currently used adsorbents for herbicide removal from the water, such as activated carbons, carbon and silica adsorbents, metal oxides, and numerous natural and industrial waste materials known as low-cost adsorbents. The adsorption capacity of these adsorbents was compared for the two most popular phenoxyacetic herbicides, 2,4-dichlorophenoxyacetic acid (2,4-D) and 2-methyl-4-chlorophenoxyacetic acid (MCPA). The application of various kinetic models and adsorption isotherms in describing the removal of these herbicides by the adsorbents was also presented and discussed. At the beginning of this review paper, the most important information on phenoxyacetic herbicides has been collected, including their classification, physicochemical properties, and occurrence in the environment.

Adsorption of 2,4-D and MCPA Herbicides on Carbon Black Modified with Hydrogen Peroxide and Aminopropyltriethoxysilane.

The carbon black N-220 surface was subjected to modification through H2O2 oxidation and deposition of aminopropyltriethoxysilane. The pristine (CB-NM) and modified materials (CB-Ox and CB-APTES) were characterized by N2 adsorption−desorption isotherms, scanning electron microscopy, energy-dispersive X-ray spectroscopy (SEM-EDS), thermogravimetry, and FTIR spectroscopy. Carbon black samples were applied as adsorbents for the removal of 2,4-dichlorophenoxyacetic acid (2,4-D) and 2-methyl-4-chlorophenoxyacetic acid (MCPA) herbicides from aqueous solutions. The influence of their surface properties on adsorption efficiency was analyzed and discussed. The results showed that the adsorption of the herbicides was pH-dependent, and the most favorable adsorption was observed in an acidic environment. The experimental data best fit pseudo-second-order and Langmuir models for kinetic and equilibrium data, respectively. The adsorption rate of both the herbicides increased in the order of CB-APTES < CB-Ox < CB-NM and was closely correlated with the mesopore volume of the carbon blacks. The monolayer adsorption capacities were found to be 0.138, 0.340, and 0.124 mmol/g for the adsorption of 2,4-D and 0.181, 0.348, and 0.139 mmol/g for the adsorption of MCPA on CB-NM, CB-APTES, and CB-Ox, respectively. The results showed that the surface chemistry of the adsorbent plays a more important role than its porous structure. Both herbicides were preferably adsorbed on APTES-modified carbon black and were adsorbed the worst on oxidized carbon black (CB-APTES > CB-NM > CB-Ox).

Electrochemical and Catalytic Properties of Carbon Dioxide-Activated Graphite Felt.

The commercial graphite felt GFA 10 was subjected to an activation process with the use of CO2 at 900 °C for 35 and 70 min. Pristine and heat-treated materials were characterized using various methods: low-temperature N2 adsorption, SEM, and EDS. Voltammetric measurements of GFA samples (before and after activation) as the working electrode were carried out. Voltammograms were recorded in aqueous solutions of 4-chlorophenol and sodium sulfate as supporting electrolyte. The catalytic activity of GFA samples in the process of 4-chlorophenol oxidation with the use of H2O2 was also investigated. The influence of graphite felt thermal activation in the CO2 atmosphere on its electrochemical and catalytic behavior was analyzed and discussed. Results of the investigation indicate that GFA activated in CO2 can be applied as an electrode material or catalytic material in the removal of organic compounds from industrial wastewater. However, the corrosion resistance of GFA, which is decreasing during the activation, needs to be refined.

Electropolymerized Aniline-Based Stainless Steel Fiber Coatings Modified by Multi-Walled Carbon Nanotubes for Electroanalysis of 4-Chlorophenol.

In this paper, a stainless steel fiber coated electropolymerized aniline, without and with carbon nanotubes (SS/PANI and SS/PANI/CNT), along with CNTs modified carbon paste electrodes (CPEs), were prepared. The electrodes were characterized by differential pulse voltammetry (DPV) and applied for the detection of 4-chlorophenol (4-CP). For all the electrodes, the oxidative peak current showed a linear dependence on the 4-CP concentration in the range of 0.05-0.5 mmol/L with R2 ≥ 0.991. SS/PANI/CNT electrodes showed greater sensitivity for the detection of the 4-CP than the SS/PANI and CPEs. For all of the aniline-based stainless steel electrodes, both the LOD and LOQ decreased with the increase in the number of electropolymerization cycles. The lowest LOD (0.38 µmol/L) and LOQ (1.26 µmol/L) were observed for the SS/PANI/CNT electrode modified in aniline solution during 30 cycles. The methods were successfully applied to the analysis of 4-CP in real samples (tap water and river water). The results demonstrated the good agreement of the added and found concentrations of the 4-CP. The recovery and precision were from 95.12% to 102.24% and from 1.53% to 6.79%, respectively. The proposed electrodes exhibited acceptable reproducibility, admirable stability, and adequate repeatability and showed potential for the analysis of 4-CP in water.

Adsorptive and Electrochemical Properties of Carbon Nanotubes, Activated Carbon, and Graphene Oxide with Relatively Similar Specific Surface Area.

Three carbon materials with a highly diversified structure and at the same time much less different porosity were selected for the study: single-walled carbon nanotubes, heat-treated activated carbon, and reduced graphene oxide. These materials were used for the adsorption of 2,4-D herbicide from aqueous solutions and in its electroanalytical determination. Both the detection of this type of contamination and its removal from the water are important environmental issues. It is important to identify which properties of carbon materials play a significant role. The specific surface area is the major factor. On the other hand, the presence of oxygen bound to the carbon surface in the case of contact with an organochlorine compound had a negative effect. The observed regularities concerned both adsorption and electroanalysis with the use of the carbon materials applied.

Adsorption of 2,4-dichlorophenoxyacetic acid and 4-chloro-2-metylphenoxyacetic acid onto activated carbons derived from various lignocellulosic materials.

Adsorption of 2,4-dichlorophenoxyacetic acid (2,4-D) and 4-chloro-2-metylphenoxyacetic acid (MCPA) from aqueous solution onto activated carbons derived from various lignocellulosic materials including willow, miscanthus, flax, and hemp shives was investigated. The adsorption kinetic data were analyzed using two kinetic models: the pseudo-first order and pseudo-second order equations. The adsorption kinetics of both herbicides was better represented by the pseudo-second order model. The adsorption isotherms of 2,4-D and MCPA on the activated carbons were analyzed using the Freundlich and Langmuir isotherm models. The equilibrium data followed the Langmuir isotherm. The effect of pH on the adsorption was also studied. The results showed that the activated carbons prepared from the lignocellulosic materials are efficient adsorbents for the removal of 2,4-D and MCPA from aqueous solutions.

Hard coal as a potential low-cost adsorbent for removal of 4-chlorophenol from water.

The potential use of raw hard coals as low-cost adsorbents for the removal of 4-chlorophenol (4-CP) from aqueous solutions was examined. The effect of experimental parameters such as the pH and salt presence was evaluated. The kinetic studies showed the equilibrium time was found to be 2 h for all of the adsorbents and that the adsorption process followed the pseudo-second order kinetic model. The adsorption isotherms of the 4-CP on the hard coals were fitted to the Langmuir, Freundlich, Langmuir-Freundlich, Sips and Redlich-Peterson equations. Based on the results obtained, hard coals appear to be a promising adsorbent for the removal of some hazardous water pollutants, like 4-CP and related compounds.

Adsorption of 2,4-Dichlorophenoxyacetic Acid from an Aqueous Solution on Fly Ash.

The adsorption of 2,4-dichlorophenoxyacetic acid (2,4-D) on fly ash was studied. The effects of adsorbent dose, contact time, pH, ionic strength, and temperature on the adsorption were investigated. Adsorption kinetic data were analyzed using pseudo-first and pseudo-second order models, and results showed that adsorption kinetics were better represented by the pseudo-second order model. Adsorption isotherms of 2,4-D on fly ash were analyzed using the Freundlich and Langmuir models. Thermodynamic parameters (ΔG°, ΔH°, and ΔS°) indicated that the adsorption process was spontaneous and endothermic. The negative values of ΔG° and the positive value of ΔH° indicate the spontaneous nature of 2,4-D adsorption on fly ash, and that the adsorption process was endothermic. Results showed that fly ash is an efficient, low-cost adsorbent for removal of 2,4-D from water.

Determination of endogenous thiols and thiol drugs in urine by HPLC with ultraviolet detection.

Analysis of urine for endogenous thiols and thiol drugs content by HPLC with ultraviolet detection is addressed. Other methodologies for detection and determination of thiols in urine are only mentioned. Outline of metabolism, role of main biological thiols in physiological and pathological processes and their reference concentrations in urine are presented. In particular, urine sample preparation procedures, including reduction of thiol disulfides, chemical derivatization and reversed-phase HPLC separation steps are discussed. Some experimental details of analytical procedures for determination of endogenous thiols cysteine, cysteinylglycine, homocysteine, N-acetylcysteine, thioglycolic acid; and thiol drugs cysteamine, tiopronin, D-penicillamine, captopril, mesna, methimazole, propylthiouracil and thioguanine are reviewed.

Reversed-phase liquid chromatography method for the determination of total plasma thiols after derivatization with 1-benzyl-2-chloropyridinium bromide.

A high-performance liquid chromatography method was developed for simultaneous detection and quantitation of total cysteine, glutathione, homocysteine and cysteinylglycine in human plasma. The two key steps in the analysis are reduction of disulfides and treatment with 1-benzyl-2-chloropyridinium bromide, which rapidly and quantitatively reacts with thiol groups to form stable S-pyridinium derivatives with intense UV absorption. The derivatives are well separated on a Zorbax SB C(18) column using reversed-phase high-performance liquid chromatography and monitored at 315 nm. The calibration graphs were linear over concentration ranges covering most experimental and clinical cases with a regression coefficients better than 0.999. The detection and quantitation limits for all analytes were 0.2 and 0.5 micromol/L, respectively. The recoveries were 99.25-101.68%. The intra- and interassay imprecisions were 0.88-4.24 and 1.68-5.14%, respectively. The method was applied for plasma samples donated by apparently healthy volunteers.

Measurement of reduced and total mercaptamine in urine using liquid chromatography with ultraviolet detection.

A simple liquid chromatographic method for the determination of reduced and total mercaptamine in human urine is described. The method is based on derivatization with 2-chloro-1-methylquinolinium tetrafluoroborate followed by ion-pairing reversed-phase liquid chromatography separation and ultraviolet-absorbance detection at 355 nm. Total mercaptamine was determined by reductive conversion of its oxidized fraction to the thiol form before the derivatization step. Baseline separation was achieved on an analytical Zorbax SB C(18) (5 microm, 150 x 4.6 mm) column with a mobile phase consisting of pH 2.0 0.05 mol L(-1) trichloroacetic acid buffer (component A) and acetonitrile (component B) pumped at 1.2 mL min(-1). Gradient elution was used: 0-3 min 12% B, 3-9 min 12-30% B, 9-12 min 30-12% B. The response of the detector was linear within the ranges studied, from 0.1 to 50 micromol L(-1) for reduced mercaptamine and from 0.4 to 400 micromol L(-1) for total mercaptamine. The imprecision ranges for reduced and total mercaptamine were within 1.45-11.71 and 0.73-10.61%, respectively. The analytical accuracy for determined compounds was from 98.79 to 109.77%. The lower limits of detection and quantitation were 0.05 and 0.1 micromol L(-1) of urine for reduced mercaptamine, and 0.2 and 0.4 micromol L(-1) of urine for total mercaptamine, respectively. This method can be used for routine clinical monitoring of the title thiol-drug and its reduced and oxidized fractions. Moreover, cysteine and cysteinylglycine can be measured concurrently, if needed.

Simultaneous determination of tiopronin and d-penicillamine in human urine by liquid chromatography with ultraviolet detection.

d-Penicillamine and tiopronin are drugs widely used for the treatment of many diseases. Because of the relatively high frequency of side effects to these compounds, some of which are dose-related, drug monitoring in urine samples during treatment is advisable. In this paper, we describe a simple method for the determination of tiopronin and d-penicillamine in human urine. The method was based on derivatization with 2-chloro-1-methylquinolinium tetrafluoroborate followed by ion-pairing reversed-phase liquid chromatography separation and ultraviolet-absorbance detection. 2-S-quinolinium derivatives of thiols were detected at 355 nm. The derivatization was optimized in terms of pH and time of the reaction. Baseline separation was achieved on an analytical Zorbax SB C-18 (5 microm, 150 mm x 4.6 mm) column with a mobile phase consisting of pH 2.0 0.09 mol L(-1) trichloroacetic acid buffer (component A) and acetonitrile (component B) pumped at 1.0 mL min(-1). Gradient elution was used: 0-4 min, 12% B; 4-8 min, 12-40% B; 8-12 min, 40-12% B. The d-penicillamine and tiopronin standards added to the urine show that the response of the detector is linear within the range studied, from 1 to 200 micromol L(-1) urine. The imprecision ranges for tiopronin and d-penicillamine were within 1.61-8.24% and 2.92-10.60%, respectively. The analytical accuracy for determined compounds was from 97.24 to 109.39%. The lower limits of detection and quantitation were 0.5 micromol L(-1) and 1.0 micromol L(-1) urine, respectively. This method can be used for routine clinical monitoring of the title thiol-drugs. Cysteine can be measured concurrently, if needed.

Determination of methimazole in urine by liquid chromatography.

A liquid chromatography methodology is developed and validated for detection and quantification of methimazole in urine. The approach is based on derivatization with 2-chloro-1-methylquinolinium tetrafluoroborate, reversed-phase high-performance liquid chromatography (HPLC) separation of so formed methimazole 2-S-quinolinium derivative from other urine matrix components, followed by detection and quantification with the use of ultraviolet-visible detector. Neither extraction, nor preconcentration of the sample are necessary. The methimazole standards added to normal urine before derivatization step show that the response of the detector, set at 345nm, is linear within the concentration range studied, that is, from 0.25 to 50mg/l urine. The relative standard deviation values for precision and recovery within the calibration range were from 1.8 to 5.0% and from 95.7 to 103.3%, respectively. Lower limits of detection and quantitation were 0.15 and 0.25mg/l urine, respectively.

Determination of total cysteamine in human plasma in the form of its 2-S-quinolinium derivative by high performance liquid chromatography.

Cysteamine (mercaptamine) can be determined in plasma by liquid chromatography with ultraviolet detection after precolumn derivatization. The plasma is reduced with sodium borohydride in order to convert disulfides to thiols, and derivatized with 2-chloro-1-methylquinolinium tetrafluoroborate. The 2-S-quinolinium derivative of cysteamine is then separated from other thiols derivatives present in the plasma, and quantitated using high-performance liquid chromatography and then detection at 355 nm. Peaks from the main plasma thiols cysteine, cysteinylglycine, glutathione and homocysteine are also observed and can be measured as needed. The cystamine standards added to the plasma before the reduction step show that the response of the detector is linear within the range studied, from 0.1 to 40 micromol/L plasma. The imprecisions at the bottom and the top of the calibration range were 11.17 and 0.8% and the inaccuracies 8.64 and 1.50%, respectively, and the lower limit of quantitation was 0.1 nmol cysteamine in 1 ml of plasma.

Urinary mesna and total mesna measurement by high performance liquid chromatography with ultraviolet detection.

We describe in this report a method for determination of mesna and total mesna in urine by high performance liquid chromatography with ultraviolet detection. The method involves a treatment of the urine sample with tri-n-butylphosphine in order to convert mesna disulfides to its reduced counterpart mesna, ultraviolet labelling with 2-chloro-1-methylquinoluinium tetrafluoroborate, reversed-phase HPLC separation, and detection and quantitation at 350nm. The result corresponds to total mesna that is sum of mesna, dimesna and its mixed disulfides with endogenous thiols. For determination of mesna the reduction step is omitted. Content of disulfide forms of mesna can be calculated by subtracting the concentration of mesna from the total mesna concentration. The separation of 2-S-quinolinium derivatives of mesna from those of endogenous urinary thiols and internal standard was achieved on an analytical Waters Nova-Pak C18 (150mmx3.9mm, 5mum) column. A mixture of an aqueous solution of pH 2.3, 0.05M trichloroacetic acid and acetonitrile (88:12, v/v) was used as a mobile phase at flow rate of 1.2ml/min and ambient temperature. The assay for mesna and total mesna in urine was proved to be linear over the studied ranges of 0.2-30 and 0.2-800nmol/ml urine, respectively. The mean recoveries over the calibration ranges were 95.4% for mesna and 99.7% for total mesna. The lower limits of detection and quantitation were 0.1 and 0.2nmol/ml for both the procedures, respectively. The imprecision did not exceed 8.5%. No interference from endogenous substances was observed.