New anion-exchange solid-phase extraction support used for preconcentration and determination of lead in water samples by flame atomic absorption spectrometry

A new chelating resin was prepared by coupling Amberlite XAD-2 with Brilliant Green through an azo spacer. The resulting resin has been characterized by FTIR spectrometry, elemental analysis, and thermogravimetric analysis and studied for the preconcentration and determination of trace Pb(II) ions from solution samples. The anionic complex of Pb(II) and iodide was retained on the resin by the formation of an ion associate with Brilliant Green on Amberlite XAD-2 in weak acidic medium. The optimum pH value for sorption of the metal ion was 5.5. The sorption capacity of the functionalized resin is 53.8 mg/g. The chelating resin can be reused for 20 cycles of sorption-desorption without any significant change in sorption capacity. A recovery of 103% was obtained for the metal ion with 0.1 M EDTA as the eluting agent. Scatchard analysis revealed that the homogeneous binding sites were formed in the polymers. The resin was subjected to evaluation through batch binding and column chromatography of Pb(II). The equilibrium adsorption data of Pb(II) on modified resin were analyzed by Langmuir, Freundlich, and Temkin models. Based on equilibrium adsorption data, the Langmuir, Freundlich, and Temkin constants were determined to be 0.192, 13.189, and 3.418 at pH 5.5 and 25 degrees C. The method was applied for lead ion determination in tap water samples.     

Studies on decontamination of spent ion exchange resin used for plutonium purification in PUREX stream

This paper deals with the studies on decontaminations of spent ion exchange resin used for purification of plutonium in PUREX process stream. Studies were carried out to optimize the chemical procedure for removal of plutonium and fission products activities form spent Ion Exchange resin. Different metal complexing reagents were tested for leaching out of radionuclides entrapped in irradiated spent ion exchange resin. The experimental results indicate that 0.01 M NaF solution was found the most suitable for removal of plutonium. The mixture of Na₂CO₃ and sodium salt of EDTA solution was found to be better for decontamination of spent ion exchange resin from beta and gamma activities. Optimized mixture of 0.5 M Na₂CO₃ and 0.1 M sodium salt of EDTA solution was found to be the most effective for fission product activities removal. After successive multiple contacts using these suitable reagents, the Pu and fission product activities in spent ion exchange resin were brought down to a minimum possible level, making it quite suitable for its long term storage.     

Untersuchungen zur adsorptiven Anreicherung von Elementspuren an Adsorberharzen

Summary Because of the purity and of the adsorption properties, the Amberlite XAD-4 resin is an adsorbent suitable for multielement preconcentration from aqueous solutions. Adsorbed trace compounds can easily be eluted from the resin by use of 1 M HNO₃ in acetone and subsequently be determined by AAS. In this paper the adsorptivity of complexes of 15 elements with different chelate forming reagents was investigated. Besides of multielement preconcentration, selective trace separation procedures are possible by suitable selection of complex reagents and pH-adjustment of the sample solution. In many cases the resin XAD-4 can advantageously be used as a trace collector instead of activated carbon. The advantages and disadvantages in the application of the two adsorbents are discussed.     

In search of higher sensitivity: Pu isotopic analysis

Summary Thermal ionization mass spectrometry (TIMS) is an effective method for isotopic and ultra-sensitivity determination of plutonium. This project aims at improving the National Institute of Standards and Technology (NIST) TIMS system sensitivity for the analysis of plutonium from environmental samples. The TIMS detection limits for direct, electrodeposition, and resin bead source loading techniques were determined by systematically varying the amount of plutonium loaded on the rhenium filament. It has been shown in our preliminary work that the resin bead could produce a stable TIMS ion beam for as long as 6 h period with ?10⁸ Pu atoms loaded onto a single resin bead.     

Photometric determination of copper with N-(dithiocarboxy)sarcosine after preconcentration with amberlite xad-2 resin

The copper(II) chelate of N-(dithiocarboxy)sarcosine (DTCS) is sorbed on a column of Amberlite XAD-2 resin from a pH-7 phosphate solution (0.1M) and stripped with a pH-9.0 ammonia solution (0.2M) in 60% methanol. The absorbance of the eluted chelate is measured at 432 nm against water. Sodium nitrilotriacetate, sodium tripolyphosphate, and EDTA can be used to mask interfering metal ions other than mercury(II), the resulting complexes not being sorbed on the resin. The mercury(II) chelate of DTCS is also sorbed on and stripped from the column along with the copper chelate, but does not interfere in the photometric determination of copper, because it is colourless. The recovery of copper(II) is quantitative from test solutions (50–500 ml) of any salinity up to that of sea-water. Concentration factors of up to about 20 are obtained. The method is highly selective for copper and can be applied to its determination in sea-water.     

Recovery and purification of plutonium in lean plutonium product stream obtained during reprocessing of fast reactor spent fuels

A method has been developed for final purification of plutonium from uranium and fission products of high beta gamma activity. This method involves selection of a suitable ion exchange resin for the purification of plutonium in order to deliver a quality PuO₂ product. The effect of the concentration of uranium and plutonium, effect of increased loading of uranium and number of bed volumes for effective washing, which are some of the parameters that generally affect the recovery and purification of plutonium were investigated. An excellent decontamination factor for fission products has been achieved by this anion exchange process which in turn delivered an excellent PuO₂ product quality in terms of purity and associated beta gamma activity with low personnel radiation exposure.     

Rapid method for the analysis of plutonium isotopes in a soil sample within 60 min.

A rapid method for the determination of Pu isotopes in a soil sample within 60 min of starting sample pretreatment was developed. The large reduction in the analysis time was attained by the rapid and perfect digestion of the sample using an alkaline fusion method with an induction heating machine. Pu concentrations were then determined by flow injection/ICP-MS using a solid extraction resin after preconcentration by batch extraction with a chelate resin. The limits of detection for 239Pu and 240Pu were 9.2 fg and 4.3 fg, corresponding to 0.03 and 0.05 Bq kg(-1), respectively, under our analytical conditions, which satisfy the lower detection limits (0.5 Bq kg(-1) of 239Pu, and 2 Bq kg(-1) of 240Pu) required for rapid analysis techniques by the Ministry of Education, Culture, Sports, Science and Technology, Japan. This method provides a powerful and practical technique for emergency monitoring in and around nuclear facilities that handle large amounts of plutonium.     

Production of mutagenic artifacts by the action of residual chlorine on XAD-4 resin

XAD resins are commonly used to recover and concentrate organics from chlorinated water. It was found that the action of residual chlorine on XAD-4 resin produced mutagenic artifacts in a dose dependent manner. The production of mutagenic artifacts could be suppressed at least ten-fold by converting free chlorine to monochloramine. Kinetic studies of the reaction between free chlorine and XAD-4 resin showed a reaction rate dependence upon pH and chloride ion concentration that suggests participation of species besides hypochlorous acid.     

非均相聚砜螯合滤膜的制备及其对Cu~(2+)的吸附性能研究

通过探讨共混比例、螯合树脂粒径及铸膜液温度对膜结构的影响 ,确定了最佳制膜工艺 ,用相转换法制备出对Cu2 + 具有大螯合容量的非均相螯合滤膜 .研究了螯合树脂颗粒粒径、盐溶液pH值和盐溶液浓度对膜螯合吸附量的影响 ,发现膜对Cu2 + 的最大吸附量可达 70 0 μg cm2 ,吸附行为满足Freundlich吸附等温式 .对膜进行动态螯合吸附测试表明该膜对Cu2 + 可实现吸附与解吸同步进行     

Speciation analysis of inorganic Sb(III) and Sb(V) ions by using mini column filled with Amberlite XAD-8 resin

The speciation of inorganic Sb(III) and Sb(V) ions in aqueous solution was studied. The adsorption behavior of Sb(III) and Sb(V) ions were investigated as iodo and ammonium pyrollidine dithiocarbamate (APDC) complexes on a column filled with Amberlite XAD-8 resin. Sb(III) and Sb(V) ions were recovered quantitatively and simultaneously from a solution containing 0.8 M NaI and 0.2 M H₂SO₄ by the XAD-8 column. Sb(III) ions were also adsorbed quantitatively as an APDC complex, but the recovery of the Sb(V)-APDC complex was found to be <10% at pH 5. According to these data, the concentrations of total antimony as Sb(III)+Sb(V) ions and Sb(III) ion were determined with XAD-8/NaI+H₂SO₄ and XAD-8/APDC systems, respectively. The Sb(V) ion concentration was calculated by subtracting the Sb(III) concentration found with XAD-8/APDC system from the total antimony concentration found with XAD-8/NaI+H₂SO₄ system. The developed method was applied to determine Sb(III) and Sb(V) ions in samples of artificial seawater and wastewater.     

On-line separation of Pu(III) and Am(III) using extraction and ion chromatography

An on-line method developed for separating plutonium and americium was developed. The method is based on the use of HPLC pump with three analytical chromatographic columns. Plutonium is reduced throughout the procedure to trivalent oxidation state, and is recovered in the various separation steps together with americium. Light lanthanides and trivalent actinides are separated with TEVA resin in thiocyanate/formic acid media. Trivalent plutonium and americium are pre-concentrated in a TCC-II cation-exchange column, after which the separation is performed in CS5A ion chromatography column by using two different eluents. Pu(III) is eluted with a dipicolinic acid eluent, and Am(III) with oxalic acid eluent. Radiochemical and chemical purity of the eluted plutonium and americium fractions were ensured with alpha-spectrometry.     

Separation and determination of <Superscript>241</Superscript>Am in urine samples from radiation workers using PC88-A and alpha spectrometry

Bioassay technique is used for the estimation of actinides present in the body based on their excretion rate through body fluids. For occupational radiation workers urine assay is the preferred method for monitoring of chronic internal exposure. Determination of low concentrations of actinides such as plutonium, americium and uranium at low level of mBq in urine by alpha spectrometry requires pre-concentration of large volumes of urine. This article deals with standardization of analytical method for the determination of ²⁴¹Am isotope in urine samples using Extraction Chromatography (EC) and ²⁴³Am tracer for radiochemical recovery. The method involves oxidation of urine followed by co-precipitation of americium along with calcium phosphate. This precipitate after treatment is further subjected to calcium oxalate co-precipitation. Separation of Am was carried out by EC column prepared by PC88-A (2-ethyl hexyl phosphonic acid 2-ethyl hexyl monoester) adsorbed on microporous resin XAD-7 (PC88A-XAD7). Am-fraction was electro-deposited and activity estimated using tracer recovery by alpha spectrometer. Ten routine urine samples of radiation workers were analyzed and consistent radiochemical recovery was obtained in the range 44–60% with a mean and standard deviation of 51 and 4.7% respectively.     

Use of amberlite XAD-7HP for the separation of Mn(II) and Mn(VII) in waters

A simple method is proposed for the determination and speciation of Mn(II) and Mn(VII) in waters utilizing a macroporous resin, Amberlite XAD-7HP. The batch method was employed and flame atomic absorption spectrometry was used in all determinations. Amberlite XAD-7HP resin was shown to retain Mn(VII) between pH 4 and 12. If the solution contains only one of the species, either Mn(II) or Mn(VII), the resin behaves selectively depending on the pH of the solution. The elution from the sorbent was realized using K₂C₂O₄ in HNO₃. The efficiency of the method was checked via spike recovery experiments. The proposed method was successfully applied to industrial wastewater samples and quantitative recoveries (≥96.0%) confirmed the accuracy of the method.     

用不同方法收集端红玉兰(Magnolia Rufidula Law et Zhou)鲜花香气的研究

利用XAD-4树脂吸附、微波加热后XAD-4树脂吸附、减压水蒸汽蒸馏加尾气吸附．乙醚浸提等方法收集端红玉兰(Magnolia rufidula Law et zhou)鲜花香气，并用色-质联用法分析。乙醚浸提方法获得的香成分最丰富，与其它方法收集的香成分基本一致。微波加热法所需样品少，收集时间短，效果良好。     

Aluminium determination in environmental samples by graphite furnace atomic absorption spectrometry after solid phase extraction on Amberlite XAD-1180/pyrocatechol violet chelating resin

A chelating resin, pyrocatechol violet (PV) immobilised on an Amberlite XAD-1180 support, was prepared and its use for the atomic absorption spectrometric determination of aluminium was investigated. The XAD-1180-PV resin was characterised by infrared spectrometry and thermal gravimetric analysis. The optimum pH value for quantitative sorption is 8-9, and desorption can be achieved by using 5.0-10.0 ml of 2 M HCl. The effects of diverse ions on the sorption and recovery of aluminium have been studied. The capacity of sorbent was 6.45±0.59 mg g⁻¹ Al XAD-1180-PV. Recoveries for aluminium from water samples were in the range 95-105%. The accuracy of procedure was confirmed by aluminium determination in certified reference materials. The method developed was applied with varying results to the analysis of natural water, haemodialysis fluids and microwave digested red wine samples from Tokat City.     

Plutonium removal from nitric acid waste streams

Separations research at the Rocky Flats Plant /RFP/ has found ways to significantly improve plutonium secondary recovery from nitric acid waste streams generated by plutonium purifications operations. Capacity and break-through studies show anion exchange with Dowex 1×4 /50–100 mesh/ to be superior for secondary recovery of plutonium. Extraction chromatography with TOPO /tri-n-octylphosphine oxide/ on XAD-4 removes the final traces of plutonium, including hydrolytic polymer.     

Determination of iron(II) and total iron in environmental water samples by flow injection analysis with column preconcentration of chelating resin functionalized with N-hydroxyethylethylenediamine ligands and chemiluminescence detection

A flow injection analysis (FIA) technique for the determination of Fe(II) and total-Fe in environmental water samples has been developed with a high sensitivity. The resin used for preconcentration of iron was the macroporous resin, Amberlite XAD-4 functionalized by N-hydroxyethylethylenediamine (HEED) groups. The technique employed was FIA by combination of on-line chelate resin preconcentration and chemiluminescence detection (CL), using brilliant sulfoflavine and hydrogen peroxide reagent solutions. The interference by coexisting Fe(III) could be eliminated by addition of 1×10⁻⁶ mol of deferrioxamine B solution. The detection limits of Fe(II) and total-Fe were 0.80 and 0.36 nmol l⁻¹ for 5.6-ml seawater samples with a concentration of 2 nmol l⁻¹. The relative standard deviations for both samples were less than ±4%. A typical analysis for Fe(II) can be performed in 7.5 min. The technique was ascertained by comparing the analytical value of total-Fe with the certified value of Fe in the reference standard seawater CASS-3.     

乙酰丙酮基聚苯乙烯在萃取金属离子上的应用

大孔的苯乙烯-二乙烯苯共聚物经氯甲基化后,分别与乙酰丙酮镍、乙酰丙酮钠和四正丁基乙酰丙酮铵三种不同的乙酰丙酮盐反应,可制得聚3-(p-乙烯苄基)戊二酮-[2,4]。其中以由乙酰丙酮镍制得的聚合物最好,除二乙烯苯外,78%左右的苯环乙酰丙酮化了。该聚合物螯合Fe~(3 )和Ni~(2 )的能力与β-二酮基高聚物相仿或稍优。还比较了此类高聚物的物理机械性能。     

Preconcentration of trace metals on Amberlite XAD-4 resin coated with dithiocarbamates and determination by inductively coupled plasma-atomic emission spectrometry in saline matrices

Preconcentration of Cd(II), Cu(II), Mn(II), Ni(II), Pb(II) and Zn(II) in saline matrices on Amberlite XAD-4 resins coated with ammonium pyrrolidine dithiocarbamate (APDC) and piperidine dithiocarbamate (pipDTC) and subsequent determination by inductively coupled plasma atomic emission spectrometry were studied. Parameters such as effect of pH, effect of HNO(3) concentration on elution of metals from resin were studied. The results show that Amberlite XAD-4 coated with APDC was more efficient in the recovery of metal ions compared with Amberlite XAD-4 coated with pipDTC, in the concentration range of 0.1-200 mug l(-1), for 1 g of Amberlite XAD-4 coated resin. The detection limits for Cd(II), Cu(II), Mn(II), Ni(II), Pb(II), Zn(II) are 0.1, 0.4, 0.3, 0.4, 0.6, 0.5 mug l(-1), respectively, for resin coated with APDC and 0.7, 1.0, 0.8, 0.9, 1.7 and 1.2 mug l(-1) for resin coated with pipDTC. The effect of diverse ions on the determination of aforesaid metals was studied. The method was applied for the determination of trace metal ions in artificial sea water and natural water samples. The results were compared with extraction AAS method.     

Nickel determination in saline matrices by ICP-AES after sorption on Amberlite XAD-2 loaded with PAN

In the present paper, a solid phase extraction system for separation and preconcentration of nickel (ng g⁻¹) in saline matrices is proposed. It is based on the adsorption of nickel(II) ions onto an Amberlite XAD-2 resin loaded with 1-(2-pyridylazo)-2-naphthol (PAN) reagent. Parameters such as the pH effect on the nickel extraction, the effect of flow rate and sample volume on the extraction, the sorption capacity of the loaded resin, the nickel desorption from the resin and the analytical characteristics of the procedure were studied. The results demonstrate that nickel(II) ions, in the concentration range 0.10–275 μg l⁻¹, and pH 6.0–11.5, contained in a sample volume of 25–250 ml, can be extracted by using 1 g Amberlite XAD-2 resin loaded with PAN reagent. The adsorbed nickel was eluted from the resin by using 5 ml 1 M hydrochloric acid solution. The extractor system has a sorption capacity of 1.87 μmol nickel per g of Amberlite XAD-2 resin loaded with PAN. The precision of the method, evaluated as the R.S.D. obtained after analyzing a series of seven replicates, was 3.9% for nickel in a concentration of 0.20 μg ml⁻¹. The proposed procedure was used for nickel determination in alkaline salts of analytical grade and table salt, using an inductively coupled plasma atomic emission spectroscopy technique (ICP-AES). The standard addition technique was used and the recoveries obtained revealed that the proposed procedure shows good accuracy.