Extraction of Organic Compounds from Aqueous Media by Amberlite XAD Resins

Abstract

Three Amberlite polymeric resins, XAD-2, XAD-4 and XAD-7, were evaluated for extraction efficiency from aqueous media of several organic compounds representing pesticides, polyaromatic hydrocarbons, phenols and phthalate esters. The three resins exhibited different extraction characteristics. The extraction efficiency of the resins was found to be dependent on pH conditions and, on the average, was best at pH7. At this pH the XAD-2 and XAD-4 resins yielded quantitative recoveries in the 90–100% range for most compounds at the 20–200ppb level. Recoveries by XAD-7 resins were lower for several compounds. The recovery of aldrin and o, p DDT under all conditions was relatively low (>68%) and showed a higher degree of variability than that obtained for the other compounds. Alkaline pH conditions were generally unfavourable for the extraction of phenolic compounds but acidification to pH2 was not found to be a necessary step for the quantitative extraction of the phenolic compounds. Acidification to pH2 further led to a decrease in the recovery of most compounds for XAD-4 resins. A combined resin column yielded extraction efficiencies comparable to the XAD-2 column at pH 7, but since the three resins possess different extraction characteristics, a mixture comprising all three is recommended for the preconcentration of organic compounds from environmental water samples containing a wide range of compounds.     

Some ion-exchange resins for anion-chromatography

The quaternary ammonium salts, n-butyltrimethylammonium iodide, 1,1,3,3-tetramethylbutyltrimethylammonium iodide, n-octadecyltrimethylammonium iodide and tri-n-dodecylmethylammonium iodide were synthesized from commercially available amines and together with n-hexadecyltrimethylammonium bromide tested for retention by a series of macroreticular resins (XAD-2, XAD-4, XAD-7, XAD-8 and XAD-11) for use as "surface" ion-exchangers in the chromatography of anions. Exchange-capacity studies of the coated resins showed that the non-polar XAD-2 and XAD-4 resins had retention characteristics superior to those of the polar resins and that pore size in the resin was more important than surface area per unit weight of resin. Tri-n-dodecylmethylammonium salts in XAD-2 gave the highest exchange capacity, with best retention under elution conditions. Columns prepared from this anion-exchanger were used to separate and analyse simple mixtures of anions (chloride, nitrate and sulphate) each within the 1-30 ppm range, by single-column operation with indirect photometric detection and also by conductivity detection with background-ion suppression. Though of use for the determination of anions in simple mixtures, the resolution and performance were generally poorer than those displayed by a commercial (Dionex) column. This is at least partly attributable to the inferior column-packing properties of the granular XAD-resin.     

An Investigation on the Concentration Efficiencies of Some Macroreticular and Ambersorb Resins Using Radio-Labelled Organic Contaminants Commonly Encountered in Water

Abstract

The extraction efficiencies of the three commercially available Ambersorb®, carbonaceous, polymeric resins, XE-340, XE-347 and XE-348 were evaluated for their use as sorbents for environmental pollutants using four model, radio-labelled water-borne organic contaminants. Their accumulation behaviour was compared with that of the thoroughly-studied Amberlite®, macroreticular XAD-2 (hydrophobic) and XAD-7 (hydrophilic) resins. These model compounds were desorbed from the resins using known volumes of commonly-used solvents to select the solvent for a particular resin(s). In this preliminary study, at <4 μg/L concentrations of the labelled compounds in aqueous solution (pH 5.78), the order of extraction efficiency of the resins was found to be XAD-2 > XAD-7 > XE-340?-347?-348 for organics. Several inherent impurities originally present in the carbonaceous resins were desorbed by solvents during elution. These resins therefore required exhaustive soxhlet purification prior to use. Most of the impurities were identified by gas chromatography/mass spectrometry.     

The OsO4F-, OsO4F2(2)-, and OsO3F3- anions, their study by vibrational and NMR spectroscopy and density functional theory calculations, and the X-ray crystal structures of [N(CH3)4][OsO4F] and [N(CH3)4][OsO3F3

The fluoride ion acceptor properties of OsO4 and OsO3F2 were investigated. The salts [N(CH3)4][OsO4F] and [N(CH3)4]2[OsO4F2] were prepared by the reactions of OsO4 with stoichiometric amounts of [N(CH3)4][F] in CH3CN solvent. The salts [N(CH3)4][OsO3F3] and [NO][OsO3F3] were prepared by the reactions of OsO3F2 with a stoichiometric amount of [N(CH3)4][F] in CH3CN solvent and with excess NOF, respectively. The OsO4F- anion was fully structurally characterized in the solid state by vibrational spectroscopy and by a single-crystal X-ray diffraction study of [N(CH3)4][OsO4F]: Abm2, a = 7.017(1) A, b = 11.401(2) A, c = 10.925(2) A, V = 874.1(3) A3, Z = 4, and R = 0.0282 at -50 degrees C. The cis-OsO4F2(2-) anion was characterized in the solid state by vibrational spectroscopy, and previous claims regarding the cis-OsO4F2(2-) anion are shown to be erroneous. The fac-OsO3F3- anion was fully structurally characterized in CH3CN solution by 19F NMR spectroscopy and in the solid state by vibrational spectroscopy of its N(CH3)4+ and NO+ salts and by a single-crystal X-ray diffraction study of [N(CH3)4][OsO3F3]: C2/c, a = 16.347(4) A, b = 13.475(3) A, c = 11.436(3) A, beta = 134.128(4) degrees, V = 1808.1(7) A3, Z = 8, and R = 0.0614 at -117 degrees C. The geometrical parameters and vibrational frequencies of OsO4F-, cis-OsO4F2(2-), monomeric OsO3F2, and fac-OsO3F3- and the fluoride affinities of OsO4 and monomeric OsO3F2 were calculated using density functional theory methods.     

Flow microcalorimetry and competitive liquid sorption II. Liquid sorption and wetting on macroreticular hydrophilic/hydrophobic networks

Three different types of polymer networks (polymer resins) were investigated by flow microcalorimetry and selective liquid sorption from 1-propanol(1)-water(2) mixtures. Type 1 network structure is formed by non-polar, non-swelling, macroporous resins (Amberlite XAD-2, Amberlite XAD-4). The composite isotherms for alcohol sorption were S-shaped. 1-Propanol is preferentially sorbed up to x₁≈0.5. Macroreticular non-ionic resins, Amberlite XAD-7 and XAD-8, represent the second type of polymer structure. These particles have a considerable extent of swelling in the binary liquid mixture and 1-propanol was preferentially sorbed by the polymer. The composite isotherms were U-shaped and exhibit maxima and minima. The third type of network structure is attached to macroreticular polar, hydrophilic ion-exchange resins (Chelite-S, Amberlyste A-21). Depending on the composition range of the binary liquid mixture, the resins may swell to a different extent and water is preferentially embeded in the porous polymer network. The swelling of the polymer networks was monitored by the gravimetric technique in separate experiments. The sorption capacity determined from the liquid uptake of the resins was related to the sorption capacity derived from the reduced surface excess. The enthalpy effect accompanying the sorption process was determined by flow and immersion microcalorimetry. The enthalpy of displacement isotherms reveals differences in polarity and swelling ability of the polymer network fairly well. Structural changes in the adsorption layers and formation of alcohol-water clusters on the surfaces play an important role.     

Preparation and characterization of chelating resins loaded with 2-(5-bromo-2-pyridylazo)-5-(diethylamino)phenol for preconcentration of rare earth elements

 Chelating resins prepared by sorption of 2-(5-bromo-2-pyridylazo)-5-(diethylamino)phenol (5-BrPADAP) on macroporous resins (Amberlite XAD-4 and XAD-7) were characterized. The adsorption properties (amount of chelating agent adsorbed per gram of resin, sorption kinetics, retention capacity, etc.) and the thermodynamic quantities of each adsorption process were determined. The retention of some rare earth elements (e.g. Er, Yb and Lu) on these chelating resins was studied in order to preconcentrate them for their determination by X-Ray fluorescence spectrometry. Received: 7 September 1995/Revised: 2 January 1996/Accepted: 10 January 1996     

STUDIES ON THE ADSORPTION OF PHENOLIC COMPOUNDS ON A PS-BASED RESIN MODIFIED BY NITRO FUNCTIONAL GROUPS

A new adsorbent (JN-01) was prepared by modifying resin NDA-1800 with nitro functional groups.The adsorption capacities of resins XAD-4,NDA-1800 and JN-01 were investigated,and the results indicated that the modified resin JN-01 was much better in adsorbing phenol,p-nitrophenol and p-cresol.The adsorption capacities of the resin JN-01 were higher than those of the resins XAD-4 and NDA-1800 within a temperature range of 283-323 K,which might be attributed to the higher surface area and the partial polarit...     

Ligand-assisted reduction of osmium tetroxide with molecular hydrogen via a [3+2] mechanism

Osmium tetroxide is reduced by molecular hydrogen in the presence of ligands in both polar and nonpolar solvents. In CHCl3 containing pyridine (py) or 1,10-phenanthroline (phen), OsO4 is reduced by H2 to the known Os(VI) dimers L2Os(O)2(mu-O)2Os(O)2L2 (L2 = py2, phen). However, in the absence of ligands in CHCl3 and other nonpolar solvents, OsO4 is unreactive toward H2 over a week at ambient temperatures. In basic aqueous media, H2 reduces OsO4(OH)n(n-) (n = 0, 1, 2) to the isolable Os(VI) complex, OsO2(OH)4(2-), at rates close to that found in py/CHCl3. Depending on the pH, the aqueous reactions are exergonic by deltaG = -20 to -27 kcal mol(-1), based on electrochemical data. The second-order rate constants for the aqueous reactions are larger as the number of coordinated hydroxide ligands increases, k(OsO4) = 1.6(2) x 10(-2) M(-1) s(-1) < k(OsO4(OH)-) = 3.8(4) x 10(-2) M(-1) s(-1) < k(OsO4(OH)2(2-)) = 3.8(4) x 10(-1) M(-1) s(-1). The observation of primary deuterium kinetic isotope effects, k(H2)/k(D2) = 3.1(3) for OsO4 and 3.6(4) for OsO4(OH)-, indicates that the rate-determining step in each case involves H-H bond cleavage. Density functional calculations and thermochemical arguments favor a concerted [3+2] addition of H2 across two oxo groups of OsO4(L)n and argue against H* or H- abstraction from H2 or [2+2] addition of H2 across one Os=O bond. The [3+2] mechanism is analogous to that of alkene addition to OsO4(L)n to form diolates, for which acceleration by added ligands has been extensively documented. The observation that ligands also accelerate H2 addition to OsO4(L)n highlights the analogy between these two reactions.     

Isolation of organic water pollutants by xad resins and carbon

The recovery efficiencies of XAD resins −2, −4, −7, and −8 and of resin mixtures were measured using distilled water samples containing 13 organic pollutants. An equal-weight mixture of XAD-4 and XAD-8 was most efficient. XAD-2 and XAD-4/8 were further terted and found effective using tapwater. Carbon was tested as a sorbent for materials not well retained by the resins. In-column solvent washing before sample sorption was found to be as effective as Soxhlet extraction for removing background impurities. Some compounds can be desorbed from carbon by in-column solvent elution; others require Soxhlet extraction. An XAD-4/8 column in series with a carbon column was used to sample 1000 1 of tapwater. Halomethanes, n-hydrocarbons, polynuclear aromatic compounds and dibenzofuran in the order of ng/l were identified using a gas chromatograph-mass spectrometer-computer system.     

Preparation of Amberlite XAD resins coated with dithiosemicarbazone compounds and preconcentration of some metal ions

The Amberlite XAD resins coated with dithiosemicarbazones were prepared and their collection behavior of metal ions from aqueous solution was investigated. Among the resins used, the reagent-loaded Amberlite XAD-7 was found to be superior for the collection of metal ions to other reagent-loaded resins used. The quantitative collection of mercury(II), palladium(II) and copper(II) was obtained from acidic medium, while cadmium(II) and lead(II) was obtained from neutral medium by the Amberlite XAD-7 resin coated with dimethylglyoxal bis(4-phenyl-3-thiosemicarbazone) (DMBS). These metal ions collected on the resin were easily eluted with a small volume of N,N-dimethylformamide as their DMBS chelates. This collection-elution method was applied to the determination of their metal ions by reversed-phase high performance liquid chromatography with a spectrophotometric detection.     

Preconcentration and determination of Ce, La and Pr by X-ray fluorescence analysis, using Amberlite XAD resins loaded with 8-Quinolinol and 2-(2-(5 chloropyridylazo)-5-dimethylamino)-phenol

8-Quinolinol (oxine) and 2-(2-(5 chloropyridylazo)-5-dimethylamino)-phenol (5ClDMPAP) were immobilized on the non ionic sorbents Amberlite XAD-4 and XAD-7. These loaded resins were used for the preconcentration of Ce, La and Pr. High preconcentration factors were obtained in each case. After the retention of these rare earths, the resins were measured as thin films by x-ray fluorescence spectrometry. Up to 50 ppm of REEs can be retained on these thin films.     

Comparisons of sorption of aquatic humic matter by DAX-8 and XAD-8 resins from solid-state (13)C NMR spectroscopy's point of view

Aquatic humic solutes were separated in parallel by the non-ionic macroporous DAX-8 and XAD-8 resins from four different fresh water sources. On average, the sorptive power of the DAX-8 resin does not differ systematically from that of the XAD-8 resin. The DAX-8 resin seems to have more precise column characteristics compared with the XAD-8 resin. There was no significant difference between the major elemental compositions of the parallel humic-solute bulks obtained by these two resins. According to the (13)C NMR spectroscopy the content and quality of aliphatic carbons, especially those representing terminal methyl groups or methylene carbons, were the most systematic and powerful discriminating factors between the humic extracts obtained by these two resins. Generally speaking the DAX-8 and XAD-8 resins seem to isolate humic-solute bulks almost equally, although the content of aliphatics is slightly greater for the former, producing mixtures with similar structural compositions for general purposes. The structural composition and quantity of the humic-solute mixture isolable with a weakly basic DEAE-cellulose anion exchange resin differs partially from any humic fraction obtained by non-ionic sorbing solids. The environmental impact was also visible on the quality of the structural fine-chemistry of the different humic isolates obtained both by the DAX-8 and XAD-8 resins.     

Adsorption equilibrium and heat of phenol onto aminated polymeric resins from aqueous solution

Aminated polystyrene resins (NDA-101 and NDA-103) were synthesized, and their adsorption performances for phenol in aqueous solution were investigated and compared with the commercial polystyrene resin (Amberlite XAD-4) and weakly basic polystyrene resin (Amberlite IRA-96). All the associated adsorption isotherms are well described by Freundlich and Langmuir equations. The results indicated that all the four resins spontaneously adsorb phenol driven mainly by enthalpy change, and their adsorption capacities, free energy changes, enthalpy changes, and entropy changes for phenol followed the same order as: NDA-101 > NDA-103 > XAD-4 > IRA-96. Surface energy heterogeneity analysis by Do's model also suggested that the surfaces of XAD-4 and IRA-96 were more homogeneous, and the better adsorption capacity and affinity of the aminated resins (NDA-101 and NDA-103) are probably due to their multiple hydrogen bonding and π–π stacking interactions with phenol molecule.     

烯烃不对称双羟化反应中TentaGel树脂支载的可回收和重复使用的OsO_4催化剂研究

合成了在烯烃不对称双羟化反应中可回收和重复使用的TentaGel支载的OsO_4 催化剂。在DMF溶剂中，TentaGel HLBr与三乙胺反应生成季铵盐，在搅拌下后者与 K_2OsO_4饱和水溶液作用24 h，过滤，得TentaGel-OsO_4催化剂，用去离子水在索 氏提取器中连续提取24 h以除去吸附在TentaGel上未键合的K_2OsO_4。 TentaGel- OsO_4催化剂在反式-二苯乙烯的不对称双羟化反应中化学产率≥80%，立体选择性 ≥93% ee，而且连续使用五次，其催化活性不变。     

化学修饰的吸附树脂对2,4,6-三氯苯酚的吸附研究

合成了用邻羧基苯甲酰基或苯甲酰基修饰的新型聚苯乙烯-二乙烯苯吸附树脂ZH-01, ZH-02和ZH-03, 利用瓶点法研究了它们和Amberlite XAD-4对288～318 K下水溶液中2,4,6-三氯苯酚的静态吸附和静态脱附特征以证实吸附质与吸附剂之间存在化学吸附, 并利用半经验分子轨道法(AM1)计算的几种吸附剂和2,4,6-三氯苯酚的前线轨道近似能级进行了解释. 结果表明: 经邻羧基苯甲酰基或苯甲酰基化学修饰后的树脂ZH-01, ZH-02和ZH-03对水溶液中2,4,6-三氯苯酚的吸附过程在合适温度时会使酚羟基和吸附剂表面的羰基发生作用, 对吸附剂进行适当的化学修饰后, 对2,4,6-三氯苯酚的穿透吸附容量均为Amberlite XAD-4树脂的150%, 饱和吸附容量是Amberlite XAD-4树脂的114％～128％.     

2-噻吩乙酸在3种树脂上的吸附行为研究

通过静态吸附实验 ,研究了XAD 4、NDA 10 0和ND 90吸附树脂对水溶液中 2 噻吩乙酸的吸附热力学及动力学特性 ,结果表明 ,2 噻吩乙酸在XAD 4树脂上是单层吸附 ,符合Langmuir等温吸附方程 ,吸附过程符合准一级动力学吸附方程 .2 噻吩乙酸在NDA 10 0和ND 90树脂上的吸附也能用Langmuir等温吸附方程表示 ,但并不只是单层吸附而主要是由毛细管凝聚和微孔填充作用造成的 ,吸附过程可分为大孔和中孔区的吸附以及微孔区的吸附两个阶段 ,两个阶段都符合准一级动力学吸附方程     

Poly（vinylpyridine） adsorbent for the removal of SIPA from its aqueous solution

Poly(vinylpyridine) WH-225 resin was prepared and characterized.Compared with the commercial hypercrosslinked adsorbent NDA-100 and macroporous adsorbent XAD-4 resins,the newly synthesized poly(vinylpyridine) WH-225 resin exhibited the highest adsorption capacity toward SIPA from aqueous solution.     

Azocalix[4]pyrrole Amberlite XAD-2: New polymeric chelating resins for the extraction, preconcentration and sequential separation of Cu(II), Zn(II) and Cd(II) in natural water samples

Two novel azocalix[4]pyrrole Amberlite XAD-2 polymeric chelating resins were synthesized by covalently linking diazotized Amberlite XAD-2 with calix[4]pyrrole macrocycles. The chelating resins were used for extraction, preconcentration and sequential separation of metal ions such as Cu(II), Zn(II) and Cd(II) by column chromatography prior to their determination by UV/vis spectrophotometry or flame atomic absorption spectrophotometry (FAAS) or inductively coupled plasma atomic emission spectroscopy (ICP-AES). Various parameters such as effect of pH on absorption, concentration of eluting agents, flow rate, total sorption capacity, exchange kinetics, preconcentration factor, distribution coefficient, breakthrough capacity and resin stability, were optimized for effective separation and preconcentration. The resin showed good ability for the separation of metal ions from binary and ternary mixture on the basis of pH of absorption and concentration of eluting agents. The newly synthesized resins showed good potential for trace enrichment of Cu(II), Zn(II) and Cd(II) metal ions, especially for Cu(II), as compared to the earlier reported resins. The synthesized resins were recycled at least 8-10 times without much affecting column sorption capacity. The presented method was successfully applied for determination of Cu(II), Zn(II) and Cd(II) in natural and ground water samples.     

一种新型除酚吸附树脂的合成及性能研究

用二氯乙烷和硝基苯作溶剂,三氯化铝等作催化剂,使氯甲基化交联聚苯乙烯和苯酚在40—125℃进行Fricdel-Crafts反应。制成一种具有较高比表面和一定极性的吸附树脂。它对废水中苯酚的吸附能力是Amberlite XAD-4树脂的两倍,其动力学性能、应用范围和抗干扰能力也较好,经50次循环使用,性能无明显变化。     

Isolierung und Anreicherung von Chlorphenoxyessigsäuren aus Wasser mit makroretikulären Adsorberharzen XAD-2 und XAD-7

Herbicide chlorophenoxy acetic acids can be isolated by the macroreticular adsorbing resins Dowex Amberlite XAD-2, XAD-4, XAD-7 and XAD-8. The adsorption of phenoxy acetic acids reaches an optimum at pH 2 and flow rates of about 5 bed-volumes per minute. Elution depends on the polarity and contact time of the eluent. A quantitative isolation of chlorophenoxy acids in the 25 ppb range in water can be achieved by adsorption at the divinylstyrolresin XAD-2 following elution with acetone. Further concentration of the eluate is possible by standard methods.