Speciation of waste water sediments

A sequential extraction procedure for waste water sediments was elaborated based on CO₂ and water extractants using supercritical fluid extraction instrumentation. The procedure gives information on water-soluble, carbonate-bound and mobile organic-bound trace metal fractions. The chemical interpretation of this procedure is comparable with the BCR recommended three-stage sequential extraction. The validation of the proposed procedure requires more detailed investigations.     

A novel approach for electromembrane extraction based on the use of silver nanometallic-decorated hollow fibers

A novel approach based on the use of nanometallic-decorated hollow fibers to assist electromembrane extraction is proposed. Microporous polypropylene hollow fibers, on which nanometallic silver was deposited, have been used for the first time as liquid membrane support in electromembrane extraction (EME). Different methods for the generation/deposition of silver nanoparticles (AgNPs) were studied. The best results were obtained with chemical reduction of silver nitrate using NaBH₄ in aqueous solution followed by direct deposition on the hollow fibers. The extraction performance of the new supports was compared with a previously developed EME procedure used for the extraction of selected non-steroidal anti-inflammatory drugs (NSAIDs), resulting in an increase in the extraction ratio by a factor of 1.2–2 with a 30% reduction in the extraction time. The new nanometallic-decorated supports open new possibilities for EME due to the singular properties of nanometallic particles, including chemical fiber functionalization.     

Role of Cyanex-272 as an extractant for uranium in the determination of rare earths by ICP-AES

A chemical separation procedure has been developed for the extraction of uranium from some of the crucially important rare earths using a novel extractant viz. Cyanex-272 (2,4,4-trimethyl pentyl phosphinic acid). The near total extraction of uranium and quantitative separation of rare earth elements has been validated using inductively coupled argon plasma - atomic emission spectrometry (ICP-AES). The recovery of some of the representative elements has been confirmed by radioactive tracer studies. The back extraction of uranium from the organic phase was carried out using a solution of 0.5M Na₂CO₃ which resulted in a near total recovery of uranium into the organic phase. These studies have enabled determination of sub ppm amounts of the analyte elements with a precision of 5% RSD utilizing prior chemical separation of rare earths from 1 g uranium samples in just three extractions with Cyanex-272.     

A robust procedure for the determination of plutonium and americium in seawater

A new procedure for the analysis of Pu and Am in large water samples is presented. In this procedure, the actinides are first preconcentrated from 200 liter water samples with combined MnO₂ and Fe(OH)₃ co-precipitation. Pu and Am are then separated from the large amount of Mn by performing a second precipitation of Fe(OH)₃ at pH 6. The final separation of Pu and Am from interfering elements and from each other is achieved with the use of a single extraction chromatographic column of TRU-ResinÔ. The -activities are then determined using -spectrometry after source preparation by CeF₃ micro co-precipitation. The procedure described is faster, simpler, more robust and gives higher chemical yields then procedures normally used for routine analysis of Pu and Am. The chemical yields of Pu and Am, when analysing 200 liter sea water samples, are between 80-85%.     

Method for the determination of131I in urine

A comprehensive radiochemical procedure for the measurement of gamma/beta activity of¹³¹I has been standarized by optimizing different steps. The procedure is mainly divided into three stages, i.e., (1) concentration of iodine using anion exchange column followed by elution; (2) extraction of iodine into CCl₄ and back extraction, and (3) precipitation as AgI. The percent chemical recovery and the lower limit of detection (LLD) were found to be 75.5±5% and 0.014 mBq/ml, respectively.     

Solvent Extraction of Rhenium(VII) for Preparation of No-Carrier-Added 186Re Saline Solution with High Specific Volume Activity

By using ¹⁸⁸Re as a radiotracer, the extraction behavior of Re(VII) by a tertiary amine extractant N-235 from HCl and the back-extraction behavior of Re(VII) by HNO₃ and ammonia were studied. A chemical separation procedure, which combined the acid alumina column and solvent extraction was established. The procedure was rapid and efficient for the separation of ¹⁸⁶Re from ¹⁸⁶W irradiated by 16 MeV deuterons. No-carrier-added ¹⁸⁶ReO₄ ^– saline solution with high specific volume activity was obtained. The overall recovery yield of ¹⁸⁶Re was about 85%.     

Optimization of a radioanalytical procedure for the determination of uranium isotopes in environmental samples

A radiochemical procedure is described for the fast and sensitive measurement of uranium isotopes in gaseous and liquid effluents of nuclear facilities. Equally, this procedure is suitable to measure uranium isotopes in all kinds of environmental samples. Uranium is leached from ashed sample materials with HNO₃, HF, and Al(NO₃)₃ solution and separated from matrix elements by extraction with trioctylphosphinic oxide and backextraction with NH₄F. After radiochemical cleaning by coprecipitation with LaF₃ and anion exchange, uranium isotopes are electroplated on stainless steel discs from HCl/oxalate solution. The preparation is measured by alpha-spectrometry using surface barrier detectors. The detection limit for 1000 minutes of counting time is 2 mBq per sample and nuclide, the chemical yield is in the range of 50 to 80%.     

Quantitation Of The Local Anesthetic Dibucaine With Gas Chromatography / Mass Spectrometry

Abstract

A chemical ionization and an electron impact GC/MS assaying approach is presented for determining dibucaine concentrations in biological fluids. Both use deuterium-labeled drug as the internal standard and rely on the same sample extraction and sample preparation procedure. Under chemical ionization conditions (CH₄), the assaying limits are in the range of 1–80 ng/ml of serum. Under electron impact conditions, the analytical range is 20–800 ng/ml. The chemical ionization procedure has been found suitable for monitoring drug levels in man. One volunteer, who received a single 5-mg oral dose, showed peak serum drug concentrations of 23 ng/ml attained 2 hr after drug administration. The biologic half-life (ß phase) was 11 hr.     

A Sequential Extraction Method Measures the Toxic Metal Content in Fly Ash from a Municipal Solid Waste Incinerator

The purpose of this research was to develop an optimized pretreatment procedure for toxic metals (Pb, Cd, Zn and Cu) content in fly ash from a municipal waste incinerator. In addition, modified sequential extraction procedures were used to characterize the chemical composition of the fly ash samples. The sequential extraction resolved the fly ash elements into the following chemical forms: soluble, exchangeable, carbonate, oxide, organic, and silicate compounds. Certified reference city waste incineration ash (BCR.176) was used as target ash samples. A H₂O₂+HNO₃+HF mixed acid digestion solution with a low temperature evaporation procedure was selected as optimal for the fly ash digestion. The digested solution was analyzed by inductively coupled plasma mass spectrometry (ICP‐MS), which effectively determined the concentrations of the toxic metal elements in BCR.176. Except for Cd, the recovery of Pb, Zn, and Cu under H₂O₂+HNO₃+HF digestion and their sequential extraction procedures were higher than 95%. The relative standard deviations (RSD) for recoveries of the four elements were within 10%. Furthermore, the sequential extraction procedure's results provided information on the potential mobility of the studied elements. Most of the Cd was bound to water‐soluble and carbonate material in the fly ash samples. Most of the Pb, Zn, and Cu was released to carbonates and bound to organic matter in the fly ash samples.     

Elemental fractionation of Si, Al, Ti, Fe, Ca, Mn, P, and Ba in five marine sedimentary reference materials: results from sequential extractions

We report on the elemental results from sequential extractions of BCSS-1 (marine sediment), MESS-1 (estuarine sediment), MAG-1 (marine mud), SCo-1 (Cody shale), and NIST-1c (argillaceous limestone) to encourage future comparisons of sequential extraction results within the marine geochemical and paleoceanographic communities. We measured Si, Al, Ti, Fe, Mn, Ca, P, and Ba in sequential de-ionized water (loosely-bound), MgCl₂ (exchangeable), acetic acid (carbonate), hydroxylammonium hydrochloride (oxide), H₂O₂ (organic), Na₂CO₃ (opal), and residual (lithogenic) leaches. The protocol and selected elements were tailored to be most relevant to paleoceanographic geochemical studies instead of to environmental studies. Our results show that the sequential extraction procedure faithfully yields elemental distributions that are consistent with individual SRM lithologies. Our results also show that the procedure is typically reproducible within approximately 15%. However, in almost all cases, the procedure suffers from a systematic under-recovery of material when compared with the certified, bulk chemical analysis, and the under-recovery appears to be related to the lithology of the SRM. Similar under-recovery appears to be typical of sequential extraction procedures as reported by other previous studies. While this is problematic in assessing closure, it does not diminish the potential of inter-lab comparisons and first-order accuracy comparisons. We found that the elemental totals for the sequential extractions of MAG-1 compared best with the certified, bulk totals, and we recommend using this SRM to facilitate future accuracy assessments and inter-lab comparisons.     

Use of polymethine dyes for the extraction separation and spectrophotometric determination of nitrophenols

The extraction of nitrophenols with polymethine dyes of the common formula R₁-(CH=CH)₃-R₂, indolium and benzothiazolium derivatives was studied. The effect of the acidity of the solution, the nature and the concentration of the dye, and the nature of the organic solvent on the formation and extraction of ion pairs of nitrophenols was examined; the optimum conditions were found. The most important chemical analytical characteristics of the ion pairs were determined. Molar absorptivities of extracts are 11.9 × 10⁴–14.3 × 10⁴ for ion pairs of trinitrophenol and 6.8 × 10⁴–10.1 × 10⁴ for ion pairs of dinitrophenol. A new procedure was developed for the extraction-photometric determination of nitrophenols in a mixture.     

Leaching Behaviour and Solid Phase Fractionation of Selected Metals as Affected by Thermal Treatment of a Polluted Sediment

Abstract

A contaminated dredged sediment was subjected to a thermal treatment at temperatures ranging from 120 to 450°C. The leaching behaviour of selected metals (Cd, Cu, Pb, Zn, Fe, Mn) was studied using NH₄OAc-EDTA extraction. In addition, solid phase fractionation was carried out by means of a sequential extraction procedure.

The NH₄OAc-EDTA extraction showed a sharp increase in metal leachability from sediments treated at intermediate temperatures (120–350°C). The metal fractionation of the solid phases at the different temperatures did not reveal relevant shifts except for Cu. The decrease of the oxidizable Cu fraction was highly correlated (P < 0.001) with the disappearance of organic matter at higher treatment temperatures. It is suggested that binding energy changes within the fractions rather than shifts between chemical forms account for the observed leaching behaviour.     

Determination of technetium-99 in environmental samples by solvent extraction at controlled valence

Distribution coefficients of technetium and ruthenium are determined under different conditions with CCl₄, cyclohexanone, and 5% tri-isooctylamine (TIOA)/xylene. A method for analyzing⁹⁹Tc in environmental samples has been developed by solvent extraction in which the valences of technetium and ruthenium are controlled with H₂O₂ and NaClO. Technetium and ruthenium which are oxidized to TcO ₄ ^– and RuO ₄ ^– by NaClO are separated by extraction with CCl₄ at pH 4. The RuO ₄ ^– is reduced to low valence and technetium is kept in the TcO ₄ ^– state with H₂O₂. Technetium, ruthenium, and other nuclides are subsequently separated by solvent extraction with cyclohexanone and 5% TIOA/xylene. The decontamination of the procedure is 1.35·10⁵ for¹⁰³Ru and 1.66·10⁵ for^110mAg. The chemical yield of technetium-99 is 55%.On leave from Institute of Atomic Energy, Beijing, China     

Determination of total PCB and dioxin by activation analysis

The analysis of PCB's and dioxins in water by activation with high energy photons is described. The substances were traced by heterochlorine. PCB and dioxins were separated selectively in the presence of a biphenyl-dibenzofurane mixture as a collector by extraction with hexane. Polar compounds were rinsed out, and chloroalkyles were evaporated. After exposure of the collector to 30 MeV bremsstrahlung it was decomposed following the Schöniger procedure. The chemical yield was measured through activity counting of¹¹C separated as¹¹CO₂ from the collecting agent, in comparison with a reference material. The chlorine yield was determined gravimetrically using a stoichiometrically well-determined reference material. A few nanograms of chlorine per millilitre are detectable whereby primary samples of 1 l or more may be treated. The described procedure can be recommended as a reference technique for analyses via chromatography/mass spectrometry. Simultaneous analyses of other halogens are planned.     

Rapid determination of 237Np in soil samples by multi-collector inductively-coupled plasma mass spectrometry and gamma spectrometry

A radiochemical procedure is developed for the determination of ²³⁷Np in soil with multi-collector inductively-coupled plasma mass spectrometry (MC-ICP-MS) and gamma-spectrometry. ²³⁹Np (milked from ²⁴³Am) was used as an isotopic tracer for chemical yield determination. The neptunium in the soil is separated by thenoyl-trifluoracetone extraction from 1 M HNO₃ solution after reducing Np to Np(IV) with ferrous sulfamate, and then purified with Dowex 1 × 2 anion exchange resin. ²³⁹Np in the resulting solution is measured with gamma-spectrometry for chemical yield determination while the ²³⁷Np is measured with MC-ICP-MS. Measurement results for soil samples are presented together with those for two reference samples. By comparing the determined value with the reference value of the ²³⁷Np activity concentration, the feasibility of the procedure was validated.     

Extraction of radiostrontium from the mixture of radionuclides in milk using dicarbolide of cobalt

The possibilities of radiostrontium extraction from milk after the isolation of radiocesium were investigated. The polyhedral complex of the type H⁺[(π-/3/-1,2-C₂B₉H₁₁)₂Co⁻], further referred to as dicarbolide-H⁺, in nitrobenzene was used for the extraction. The increase of values and larger differentiation of distribution ratios in the extraction of ion associates of radionuclides were achieved by hydrophobizing with polyethyleneglycol (PEG). The changes of the distribution ratios of⁹⁰Sr,⁸⁹Sr and⁹⁰Y with PEG concentration were studied, and ranges of the highest synergic effect, changing with different extraction agent concentrations in extraction from water solutions and a fresh milk were determined. The influence of milk dilution and nitric acid concentration upon the value of distribution ratio in radiostrontium extraction using dicarbolide-H⁺ and the optimum PEG concentration were investigated. Under suitably selected conditions of radiostrontium isolation, the distribution ratios of some potential contaminants were determined. The influence of nonisotopic carrier Ca²⁺ upon radiostrontium extraction was examined. The possibilities of purification of isolated radiostrontium using reextraction were investigated. A selective and quick analytical procedure was suggested for radiostrontium isolation after the separation of radiocesium from a mixture of fission and activated radionuclides in milk using extraction by dicarbolide-H⁺. The chemical yield is about 98% and⁹⁰Sr is determined by liquid scintillation technique.     

Sensory monitoring of the native state of natural waters

A procedure has been proposed for express assessment of the degree of pollution of melt and snow waters with volatile aromatic compounds using a set of chemical sensors. The number of measuring units has been minimized to 2 for the yes/no detection (alarm system) of volatile aromatic toxicants in natural waters of different salinities. An algorithm has been developed for the extraction of analytical information on the presence of volatile compounds or salts in meltwater by the sorption efficiency parameters A _ij and their profiles (petal diagrams) or by cluster analysis.     

Analysis of low-level 129I in brine using accelerator mass spectrometry

An improved solvent extraction procedure for iodine separation from brine samples has been applied at Xi’an Accelerator Mass Spectrometry (AMS) center. Oil in the brine sample has to be removed to avoid appearance of the third phase during solvent extraction and to improve the chemical yield of iodine. The small amount of oil remained in the water phase was first removed by phase separation through settling down sufficiently based on their immiscibility, and then by filtration through a cellulose filter, on which oil was absorbed and removed. After oil removed, extraction recovery of iodine could achieve more than 90 %. The sodium bisulfite as an effective reductant should be added before acidification to avoid loss of iodine by formation of I₂ in sample via reaction of iodate and iodide at pH 1–2, and then pH was adjusted to 1–2 to reduce the iodate to iodide followed by oxidation of iodide to I₂ and solvent extraction to separate all inorganic iodine. As a pre-nuclear era sample, ¹²⁹I/¹²⁷I ratio in brine is normally more than two orders of magnitude lower than that in present surface environmental samples, so prevention of cross-contamination and memory effect in apparatus during processing procedure are very critical for obtaining reliable results, and monitoring the procedure blank is very important for analytical quality of ¹²⁹I. The ¹²⁹I/¹²⁷I isotopic ratio in the brine samples and procedure blank of iodine reagents were measured to be (1.9–2.7) × 10^?13 and 2.08 × 10^?13, respectively, 3–4 orders of magnitudes lower than that in environmental samples in Xi’an, and the result of procedure blank is in the same level as the previous experiments in past 3 years, indicating contamination is not observed in our method.     

利用过硫酸钠化学抽取制备脱锂态电极材料

介绍了一种通过常规化学反应制备锂离子电池脱锂态电极材料的方法。首先将氧化剂Na₂S₂O₈与锂离子电池电极材料混合于去离子水中,对混合液进行振荡和搅拌,使脱锂反应充分进行,获得不溶于水的脱锂态电极材料和溶于水的其他生成物,然后将溶于水的生成物过滤掉,最后对不溶于水的脱锂态电极材料进行反复清洗并干燥,便获得所需材料。此方法操作简便,容易控制,计算锂含量方便准确,并且可以得到足够量和纯净的脱锂态电极材料,克服了充放电法制备和采用其他氧化剂进行化学     

Evaluation of some Isolation Methods for Organomercury Determination in Soil and Fish Samples by Capillary Gas Chromatography—Atomic Fluorescence Spectrometry

Abstract

Three extraction methods, acidic KBr/CuSO₄ isolation-methylene chloride extraction. acidic KBr/CuSo₄ isolation-methylene chloride extraction with an alkaline digestion pretreatment, and an extration method at a milder condition with citrate buffer and dithizone in chloroform, were studied for methylmercury and ethylmercury determination in soils, sediments and fish samples by the recently developed capillary gas chromatography—atomic fluorescence spectrometry system (GC-AFS). The acidic KBr/CuSO₄-methylene chloride extraction and the acidic KBr/CuSO₄-methylene chloride extraction with an alkaline digestion pretreatment were shown to be the effective methods for soils/sediments and fish samples analysis, respectively. The presence of ethylmercury species in soils of the Florida Everglades, observed with the acidic KBr/CuSO₄ isolation and methylene chloride extraction procedure, was further confirmed with the dithizone complexation/extraction procedure. The GC-AFS analytical method offers high senstivity and selectivity for the determination of organomercury halides. The GC column maintenance, a critical step for organomercury halides analysis using GC, is also discussed.