Sorption behaviour of bifenthrin on cork

Biphentrin, a known pyrethroid, was studied, aiming its removal from aqueous solutions by granulated cork sorption. Batch experiments, either for equilibrium or for kinetics, with two granulated cork sizes were performed and results were compared with those obtained with of activated carbon sorption. Langmuir and Freundlich adsorption isotherms were obtained both showing high linear correlations. Bifenthrin desorption was evaluated for cork and results varied with the granule size of sorbent. The results obtained in this work indicate that cork wastes may be used as a cheap natural sorbent for bifenthrin or similar compounds removal from wastewaters.     

Preconcentration of lead complexed with O,O-diethyl-dithiophosphate by column solid-phase extraction using different sorbents in a flow injection system coupled to a flame atomic absorption spectrometer

A comparative study of C(18) immobilized on silica, activated carbon and a polyurethane foam, as sorbents for Pb complexed with O,O-diethyl-dithiophosphate in a flow injection preconcentration system is reported. The complex was formed in 1.0 M HCl medium and processed in a simple system using a peristaltic pump, a manual injector-commutator and a mini-column filled with the sorbent. Using ethanol as eluent, the richest 150-mul fraction was collected and measured (after discarding 150, 200 and 0 mul for the activated carbon, foam and C(18), respectively) by flame atomic absorption spectrometry. The optimum concentration of the complexing agent was 0.05% m/v for C(18) and 0.2% m/v for the activated carbon and the polyurethane foam. The best sample loading flow rate was 4.0 ml min(-1) for the activated carbon and 2.0 ml min(-1) for C(18) and the polyurethane foam, while the best elution flow rate was 1.0 ml min(-1) (activated carbon) and 0.6 ml min(-1) (C(18) and foam). It was found that beyond a certain loading sample volume, for a constant analyte mass, the signal decreased. The maximum loading sample volume, for a constant analyte mass, before the signal started to decrease, was 50 ml for the activated carbon and 150 ml for the other materials. By processing 25 ml, the enrichment factors were 23, 55 and 166 for the activated carbon, foam and C(18), respectively. The best limit of detection (3sigma) was 0.3 mug l(-1) for the C(18) (1.2 mug l(-1) for the foam and 3 mug l(-1) for the activated carbon). As shown, the C(18) has a much superior retention performance in comparison to the other two materials.     

Fixation of XAD-4 power on filter paper using methyl cellulose for the passive air sampling of semi-volatile organic compounds in indoor air

The sorption capacity of a substrate serving as sampling medium can be enhanced by adding another sorbent to its surface. This is usually achieved through an impregnation process by repeated dipping of the substrate in a slurry solution containing the powder of the sorbent. Because the impregnation process only deposits the sorbent powder on the surface of the substrate, the powder could detach and fall off during field deployment. In this study, a novel approach was explored to fix the added sorbent powder to the surface of the substrate. Methylcellulose (MC) in fine crystal form was selected as the fixing agent to secure the powder of polystyrene-divinyl benzene copolymer resin (XAD-4), with its high sorption capacity, to a cellulose filter paper (CFP). The process involved first mixing XAD-4 and MC in the presence of water to form a milky slurry solution that was then painted on to the surface of the paper and then allowed to dry. The painting technique resulted in a good reproducibility of the applied amount of XAD-MC mixture with a relative standard deviation (RSD) of 12% (n = 5). Scanning electron microscope (SEM) images showed that the XAD-4 powder was held to the surface of the filter paper. No free XAD powder was dislodged from the coated filter paper when coated paper was flicked with a finger. For use as an indoor passive air sampler (PAS), this new sampling medium was placed in a round housing made of electronically polished aluminium material and was tested for uptake of polybrominated diphenyl ethers and phthalic acid dialkylesters. Surface area specific uptake rates (ASUR) of PBDEs ranged from 1.14 to 2.82 m³/(dm²d), while ASUR of phthalates had a wider range from 2.74 to 5.66 m³/(dm²d).     

Fabrication and Characterization of Diatomite-supported Activated Carbon Functional Ceramic

Using porous diatomite ceramic as carrier and phenolic resin as carbon precursor, the activated carbon functional ceramic with the activated carbon fixed into porous ceramic was prepared by the impregnation load phenolic resin, carbonization and activation isolated air. The influences of impregnation, curing, carbonization, activation etc. on the material property were discussed. The iodine value, SEM, elemental analyzer, BET and spectrum analysis chart were used to characterize the microstructures and performance of material at different conditions. The results showed that the excellent comprehensive property of activated carbon functional ceramic was gained when it adsorbed phenolic resin in 4 h under vacuum condition at curing temperature of 150 ℃ for 0.5 h and carbonization temperature of 600 ℃ for 1.0 h, and then put into 25wt% KOH for 4.0 h at activation temperature of 700 ℃ for 1.5 h. The iodine value is 176.9 mg/g, the specific surface area can reach 86.3 m2/g and the yield of carbonization is 50.48%.     

固相微萃取活性炭涂层萃取头的制备及其对卤代烃化合物的萃取

利用自制的有机硅树脂胶粘剂和粉状活性炭制成活性炭涂层萃取头。该萃取头富集能力强,对氯仿、四氯化碳、三氯乙烯、四氯乙烯4种卤代烃化合物的富集率达到13.8~18.7倍;热稳定性好,最高使用温度可达290 ℃;使用寿命长,250 ℃解吸条件下可反复使用140次以上。上述4种化物固相微萃取-气相色谱分析的结果表明,方法的最低检出质量浓度为0.008~0.05 μg/L。采用该萃取头对含有该4种卤代烃化合物的实际水样进行了SPME-GC分析,4种化合物的回收率为95.5%~104.6%。     

Determination of trace quaternary ammonium surfactants in water by combining solid-phase extraction with surface-assisted laser desorption/ionization mass spectrometry.

This study demonstrates the feasibility of combining solid-phase extraction (SPE) with surface-assisted laser desorption/ionization (SALDI) mass spectrometry to determine trace quaternary ammonium surfactants in water. The trace surfactants in water were directly concentrated on the surface of activated carbon sorbent in SPE. The activated carbon sorbent was then mixed with the SALDI liquid for SALDI analysis. No SPE elution procedure was necessary. Experimental results indicate that the surfactants with longer chain alkyl groups exhibit higher sensitivities than those with shorter chain alkyl groups in SPE-SALDI analysis. The detection limit for hexadecyltrimethylammonium bromide is around 10 ppt in SPE-SALDI analysis by sampling 100 mL of aqueous solution, while that of tetradecyltrimethylammonium bromide is about 100 ppt. The detection limit for decyltrimethylammonium bromide and dodecyltrimethylammonium bromide is in the low-ppb range.     

Removal of heavy metals from industrial wastewaters using amine-functionalized nanoporous carbon as a novel sorbent

Nano-porous carbon (NPC) was synthesized by hydrothermal condensation of fructose and characterized by X-ray powder diffraction and also nitrogen adsorption analysis. It was then modified with amino groups and used as a sorbent for the removal of heavy metal ions. The formation of amino-modified NPC was confirmed by X-ray powder diffraction, infrared spectroscopy, thermogravimetric and elemental analysis. NPC was applied for removal of Pb(II), Cd(II), Ni(II) and Cu(II) ions. The effects of sample pH and the adsorption kinetics were studied, and the adsorption capacity was determined. The sorbent was applied to the removal of heavy metal ions in industrial waste water samples.

Elution behavior of polyethylene and polypropylene standards on carbon sorbents

The elution behavior of linear polyethylene and isotactic, atactic and syndiotactic polypropylene was tested using three different carbon column packings: porous graphite (Hypercarb), porous zirconium oxide covered with carbon (ZirChrom-CARB), and activated carbon TA 95. Several polar solvents with boiling points above 150°C were selected as mobile phases: 2-ethyl-1-hexanol, n-decanol, cyclohexylacetate, hexylacetate, cyclohexanone, ethylene glycol monobutyl ether and one non-polar solvent, n-decane. Polyethylene standards were completely or partially adsorbed in all tested sorbent/solvent systems. Polypropylene standards were partially adsorbed on Hypercarb and carbon TA95, but did not adsorb on ZirChrom-CARB. ZirChrom-CARB retained polyethylene pronouncedly when 2-ethyl-1-hexanol, cyclohexylacetate or hexylacetate were used as mobile phases at temperature 150 or 160°C, while all three basic stereoisomers of polypropylene eluted in size exclusion mode in these sorbent/solvent pairs. This is very different from the system Hypercarb/1-decanol, which separated polypropylene according to its tacticity. The opposite elution behavior of polyethylene and polypropylene in system ZirChrom-CARB/2-ethyl-1-hexanol (polypropylene eluted, polyethylene fully adsorbed) enabled to realize separation of blends of polyethylene and polypropylene. Ethylene/1-hexene copolymers were separated according to their chemical composition using system Hypercarb/2-ethyl-1-hexanol/1,2,4-trichlorobenzene.     

Iron(III) Oxide Graphite Composite Electrodes: Application to the Electroanalytical Detection of Hydrazine and Hydrogen Peroxide

Composite electrodes based on iron(III) oxide, Fe₂O₃, carbon powder and epoxy resin have been prepared and characterized using electrochemical methods and X‐ray photoelectron spectroscopy (XPS). Initially composite electrodes were made by mixing micron sized carbon powder surface with iron(III) oxide. However, the voltammetric responses were unsatisfactory. Therefore, a new type of composite electrodes was made using carbon powder modified with iron(III) oxide via a wet impregnation procedure. This technique involves saturation of the carbon powder with iron(III) nitrate followed by thermal treatment at ca. 623 K forming iron(III) oxide on the surface of the carbon powder.     

Effect of oxidation of activated carbon on its enrichment efficiency of metal ions: comparison with oxidized and non-oxidized multi-walled carbon nanotubes

The effect of oxidation of activated carbon (AC) with various oxidizing agents (nitric acid, hydrogen peroxide, ammonium persulfate) on preconcentration of metal ions (Cr3+, Mn2+, Pb2+, Cu2+, Cd2+ and Zn2+) from environmental waters prior to their flame atomic absorption spectroscopic analysis was investigated. The highest recoveries and adsorption capacities towards metal ions were achieved when using nitric acid-oxidized AC (sorbent AC-NA) as preconcentrating sorbent at pH 9. A preconcentration procedure was optimized using AC-NA as sorbent, which was then compared with non-oxidized AC in terms of analytical performance of the preconcentration method. Higher sensitivity, lower detection limits and wider linear ranges were achieved when AC-NA was used. The analytical performance of the method using AC-NA as preconcentrating sorbent was also compared with nitric acid-oxidized multi-walled carbon nanotubes (sorbent MWCNT-NA) and non-oxidized multi-walled carbon nanotubes (sorbent MWCNT). The analytical performance of the preconcentration method using AC-NA was close to MWCNT-NA, but AC-NA was better than non-oxidized MWCNT. Application of the optimized preconcentration method (using AC-NA sorbent) to environmental waters (tap water, reservoir water, stream water) gave spike recoveries of the metals in the range 63-104%.     

Determination of gold in ore by flame atomic absorption spectrometry with flow-injection on-line sorbent extraction preconcentration

Gold in ores was determined by flame atomic absorption spectrometry following on-line preconcentration by sorbent extraction in a flow-injection system. The medium polarity adsorption resin Amberlite XAD-8 packed in a 220-μl micro-column was used to collect gold(III) from hydrochloric acid sample solutions for 40 s at 7.6 ml/min. Ethanol was used to elute the adsorbed analytes into the nebulizer. Optimization studies were made on sample loading rate, elution rate and sample acidity. Some possible interferences on the determination are discussed. A 35-fold enrichment was achieved at a sampling frequency of 60 h^?1 and with an RSD of 1.4%. The detection limit (3σ) and 2 μg l^?1. Results for gold in ore samples showed good agreement with those obtained using activated carbon adsorption preconcentration. The recoveries were 97–108%.     

Frequency‐Response Evidence for Parallel Diffusion Processes in the Bimodal Micropore System of an Activated Carbon

The rates of mass transport of gases such as propane, carbon dioxide, and ammonia have been studied in an activated carbon sorbent. The frequency‐response (FR) method was used to measure these rates. Small‐angle X‐ray scattering (SAXS) and nitrogen‐adsorption isotherm at 77 K showed that the activated carbon contains small micropores with diameters around 0.64 and 0.92 nm, respectively. The FR‐rate spectra distinguished two parallel diffusion processes with different time constants, suggesting that the smaller and the larger micropores were not interconnected.     

Sequestration of naphthenic acids from aqueous solution using β-cyclodextrin-based polyurethanes

The sorption characteristics of naphthenic acids (NAs) in their anion form with β-cyclodextrin (β-CD) based polyurethanes, as sorbents, from aqueous solutions that simulate the conditions of oil sands process water (OSPW) are presented. The copolymer sorbents were synthesized at various β-CD:diisocyanate monomer mole ratios (e.g., 1:1, 1:2, and 1:3) with diisocyanates of variable molecular size and degree of unsaturation. The equilibrium sorption properties of the copolymer sorbents were characterized using sorption isotherms in aqueous solution at pH 9.00 with electrospray ionization mass spectrometry to monitor the equilibrium unbound fraction of anionic NAs in the aqueous phase. The copolymer sorbents were characterized in the solid state using (13)C CP-MAS NMR spectroscopy, IR spectroscopy and elemental analysis. The sorption results of the copolymer sorbents with anion forms of NAs in solution were compared with a commercially available carbonaceous standard: granular activated carbon (GAC). The monolayer sorption capacities of the sorbents (Q(m)) were obtained from either the Langmuir or the Sips isotherm model used to characterize the sorption characteristics of each copolymer sorbent. The estimated sorption capacity for GAC was 142 mg NAs per g sorbent whereas the polymeric materials ranged from 0-75 mg NAs per g sorbent over the experimental conditions investigated. In general, significant differences in the sorption capacities between GAC and the copolymer sorbents were related to the differences in the accessible surface areas and pore structure characteristics of the sorbents. The Sips parameter (K(eq)) for GAC and the copolymer materials reveal differences in the relative binding affinity of NAs to the sorbent framework in accordance with the synthetic ratios and the value of Q(m). The diisocyanate linker plays a secondary role in the sorption mechanism, whereas the β-CD macrocycle in the copolymer framework is the main sorption site for NAs because of the formation of inclusion complexes with β-CD.     

Liquid chromatography-electrospray ionization isotope dilution mass spectrometry analysis of paraquat and diquat using conventional and multilayer solid-phase extraction cartridges

The performance of alkyl-silica sorbent packed solid-phase extraction (SPE) cartridges and a mixed-mode, polymeric sorbent packed SPE cartridge (resin SPE cartridge) were evaluated for the sample preparation of paraquat and diquat in environmental water and vegetation matrices. Also the recoveries of the native and 2H-labeled paraquat and diquat were correlated to validate that the 2H-labeled species can be used for the isotopic dilution mass spectrometry (IDMS) analysis of paraquat and diquat. The results show that the extraction efficiency of alkyl-silica SPE is dependent on the carbon loading of the sorbent and deteriorates with an increasing sample pH. The resin SPE cartridge required no pH adjustment and showed excellent correlation between the native and 2H-labeled species, therefore, allowing us to develop the first liquid chromatography-electrospray ionization IDMS analytical method for the analysis of paraquat and diquat in environmental water and vegetation matrices. Method detection limits derived using standard EPA protocol were 0.2 and 0.1 microg/l for paraquat and diquat in water matrices, and 0.02 and 0.01 microg/g in vegetation matrices, respectively.     

Removal of Cr(VI) from Aqueous Solution Using Activated Cow Dung Carbon

Removal of hexavalent chromium from aqueous medium by using activated cow dung carbon was studied. Cow dung was carbonized and activated by treating with concentrated H(2)SO(4) followed by heating for 24 h at 120 degrees C. The extent of adsorption was studied as a function of pH, contact time, amount of adsorbent, concentration of adsorbate, and temperature. At lower pH (<3.5), the prepared sorbent was capable of removing approximately 90% Cr(VI) at 5 ppm concentration from aqueous synthetic solution. The dynamics of migration of the sorbate ions from the bulk onto the sorbent surface was studied and the results obtained under various experimental conditions were found to follow standard adsorption isotherms. The reaction kinetics was found to be of first order. Copyright 2000 Academic Press.     

Speciation of some trace elements in water samples after preconcentration on activated carbon by neutron activation analysis

A new filtering column has been developed on the covalent attachment of chelating functionalities to simple, highly hydrophilic adsorbent material, which can then complex heavy metal ions irreversibly and targeted towards toxic metals removal. The capacity of the chemically modified sorbent (modified charcoal) materials used in this work was evaluated for the above mentioned heavy metal ions in the presence of iron ions and simulated water samples. The methods are based on preconcentrations of the elements of interest on activated carbon and zirconium loaded activated carbon using specific conditions of pH and oxidation states followed by a final determination by neutron activation analysis (NAA). It has been investigated that zirconium loaded activated carbon is able to adsorb As (V), Se (VI), Cr (VI) and Hg (II) at any pH while activated carbon is able to adsorb As (III), Se (IV), Cr (III) and Hg(I) at higher pH. This revised version was published online in August 2006 with corrections to the Cover Date.     

Manganese dioxide graphite composite electrodes: application to the electroanalysis of hydrogen peroxide, ascorbic acid and nitrite.

The modification of carbon powder with manganese dioxide using a wet impregnation procedure with electrochemical characterisation of the modified powder is described. The process involves saturation of the carbon powder with manganese(II) nitrate followed by thermal treatment at ca. 773 K leading to formation of manganese(IV) oxide on the surface of the carbon powder. The construction of composite electrodes based on manganese dioxide modified carbon powder and epoxy resin is also described, including optimisation of the percentage of the modified carbon powder. Composite electrodes showed attractive performances for electroanalytical applications, proving to be suitable for the electrochemical detection of hydrogen peroxide, ascorbic acid and nitrite ions with limits of detection comparable to the detection limits achieved by other analytical techniques. The results obtained for detection of these analytes, together with composite electrodes flexible design and low cost offers potential application of composite electrodes in biosensors.     

Desulfurization of liquid fuels by adsorption on carbon-based sorbents and ultrasound-assisted sorbent regeneration

Several carbon-based adsorbents, CuCl/AC, PdCl2/AC, and Pd/AC (where AC denotes activated carbon), were studied for desulfurization of a model jet fuel by selective adsorption of thiophenic molecules. Comparisons with gamma-Al2O3 support and desulfurization of a commercial jet fuel were also studied. The results showed that the selective sulfur adsorption capacity of PdCl2 was higher than that of CuCl and Pd(0), in agreement with molecular orbital results. It was also found that the activated carbon is the best support for pi-complexation sorbents to remove sulfur-containing compounds, i.e., benzothiophene and methylbenzothiophene. Among all the adsorbents studied, PdCl2/AC had the highest capacity for desulfurization. A significant synergistic effect was observed between the carbon substrate and the supported pi-complexation sorbent, and this effect was explained by a geometric effect. The saturated sorbent was regenerated by desorption assisted by ultrasound with a solvent of 30 wt % benzene and 70 wt % n-octane. The results showed that the amount of sulfur desorbed was higher with ultrasound, 65 wt % desorption vs 45 wt % without ultrasound in a static system at 50 degrees C.     

Flow-injection determination of total organic fluorine with off-line defluorination reaction on a solid sorbent bed

Considering recent reports on widespread occurrence and concerns about perfluoroalkyl substances (PFAS) in environmental and biological systems, analysis of these compounds have gained much attention in recent years. Majority of analyte-specific methods are based on a LC/MS/MS or a GC/MS detection, however many environmental or biological studies would benefit from a total organic fluorine (TOF) determination. Presented work was aimed at developing a method for TOF determination. TOF is determined as an amount of inorganic fluoride obtained after defluorination reaction conducted off-line using sodium biphenyl reagent directly on the sorbent without elution of retained analytes. Recovered fluoride was analyzed using flow-injection system with either fluorimetric or potentiometric detection. The TOF method was tested using perfluorocarboxylic acids (PFCA), including perfluorooctanoic acid (PFOA), as model compounds. Considering low concentrations of PFAS in natural samples, solid-phase extraction as a preconcentration procedure was evaluated. Several carbon-based sorbents were tested, namely multi-wall carbon nanotubes, carbon nanofibres and activated carbon. Good sorption of all analytes was achieved and defluorination reaction was possible to carry out directly on a sorbent bed. Recoveries obtained for PFCAs, adsorbed on an activated carbon sorbent, and measured as TOF, were 99.5 ± 1.7, 110 ± 9.4, 95 ± 26, 120 ± 32, 110 ± 12 for C4, C6, C8, C10 and C12-PFCA, respectively. Two flow systems that would enable the defluorination reaction and fluoride determination in a single system were designed and tested.     

炭基载体对超声加压浸渍法制备锌基脱硫剂中温硫化性能的影响

以活性炭(AC)、褐煤半焦(LSC)、烟煤半焦(BSC)和褐煤焦(LC)4种炭基材料作为载体,利用超声辅助加压浸渍法分别制备了氧化锌炭基系列中温煤气脱硫剂。借助固定床硫化反应测试装置、氮气吸附、XRD和SEM等手段对4种脱硫剂的脱硫性能、物相组成、比表面积和孔结构进行了测试和表征。结果表明,超声辅助加压浸渍法能够有效改善炭基材料的孔隙结构,加压水热处理后的褐煤半焦比表面积可增大为原来的11倍;炭基材料种类不会影响氧化锌炭基脱硫剂中活性组分的赋存形态,但直接影响活性组分的上载率及其在载体表面分散的均匀性,进而影响脱硫剂的中温硫化性能。褐煤半焦制备的脱硫剂Zn/LSC中较高的活性组分利用率和丰富的孔隙结构使其脱硫效果最佳,脱硫精度达到99.99%时的穿透时间和实际硫容分别达到11.0 h和5.17%。褐煤半焦孔结构最易于改性,是加压水热合成中温煤气脱硫剂的一种优良的载体材料,这也是资源相对丰富的褐煤有效利用的途径之一。