The analysis of biological and environmental samples for lead by photon activation

Résumé On utilise le réaction photonucléaire²⁰⁴Pb(γ, n)²⁰³Pb pour doser le plomb dans des échantillons issue de milieux biologiques et de l'environment. En utilisant des échantillons déjà titrés en plomb par d'autres méthodes, on a jugé la précision des mesures convenable. En utilisant une séparation chimique soignée après l'irradiation, la quantité limite détectée est de l'ordre d'une dizaine de nanogrammes.      

Spectrophotometric analysis of trichloroethylene in various environmental and biological samples

A simple sensitive extractive spectrophotometric method for determination of trichloroethylene is proposed. Trichloroethylene is treated with pyridine to form glutaconic aldehyde by heterolytic cleavage of the pyridine ring. Glutaconic aldehyde is further coupled with 4-aminoacetanilide to form an orange–red dye which is extractable in 3-methyl-1-butanol. The extracted dye shows absorption maximum at 520 nm. The system obeys Beer’s law in the range of 0.05–0.8 μg mL^?1. Important analytical parameters such as time, temperature, reagent concentration, acidity etc. have been optimized for complete colour reaction. Sandell’s sensitivity and molar absorptivity for the system were found to be 0.001 μg cm^?2 and 1.2 × 10⁵ L mol^?1 cm^?1, respectively. The proposed method is satisfactorily applied to micro-level determination of trichloroethylene in various environmental and biological samples.     

A new adsorbent for trace organic analysis in environmental samples

Summary Graphite fluoride has been evaluated as an adsorbent for use in concentrating organic impurities in air and water samples. This material has been shown to yield large breakthrough volumes for most organics and should be useful for trace analysis in environmental chemistry.     

Total dissolution of environmental and biological samples by closed-vessel microwave digestion for radiometric analysis

Dry soil, fish-fillet ash, and grass ash were dissolved with a closed-vesselmicrowave oven system and mineral acids. Reagents and dissolution conditionswere varied to ensure total dissolution and recovery of radionuclides. Solventsto dissolve 99.9% of the mass of 3 g samples satisfactorily were 45 ml 14NHF followed by 60 ml 4N HNO₃ saturated with H₃BO₃ for soil, 60 ml 9N HNO₃ followed by 60 ml 14N HF for grass,and 60 ml 9N HNO₃ for fish. The reliability of the dissolutionwas tested with samples from the DOE Quality Assurance Program.     

A new and sensitive method for the spectrophotometric determination of ethion in environmental and biological samples

A new and sensitive spectrophotometric method is described for the determination of sub ppm levels of the organophosphorus pesticide ethion based on the oxidation of ethion by potassium permanganate in phosphoric acid to sulphones and its hydrolysis under acidic condition at 100°C to release formaldehyde, which is then determined by a reaction with 1,3,5-trihydroxybenzene (phloroglucinol) in alkaline medium. Beer's law is obeyed in the range of 0.1–0.8 ppm of ethion at 460 nm. The analytical parameters have been optimized.     

Applications of solid-phase microextraction to chemical analysis of live biological samples

This work reviews some recent applications of solid-phase microextraction (SPME) for the chemical analysis of live biological samples. Application of SPME to microbiological analysis, organic volatile compounds emitted by vegetables and insect semiochemicals will be discussed. A short discussion on the principles and the basic parameters of SPME is also included.     

Trends in speciation analysis of vanadium in environmental samples and biological fluids--a review

A comprehensive review is presented addressing recent trends in the speciation and determination of vanadium in environmental and biological sample matrices, including important analytical aspects such as sample clean up, pre-concentration and method development. Methodology based on both separation and spectroscopic techniques for the determination of vanadium speciation is discussed. A brief outline of analytical principles, together with an overview of the recent developments and applications of vanadium speciation determination is included. The newer methods for detecting metal ions including hyphenated spectroscopic techniques and sample preparation schemes are also discussed.     

离子液体在环境与生物样品分析中的应用及研究进展

离子液体作为一类安全稳定、环境友好的新型介质,因其具有别于传统挥发性有机溶剂的独特的性质,开始用于化学研究的很多领域.在分析检测中,离子液体的研究主要集中在分离富集、电化学分析与传感器、光谱与质谱等方面.本文评述了离子液体在这些领域的应用,并对其前景进行了展望.     

Analytical methodology for speciation of arsenic in environmental and biological samples

A literature search on the speciation of arsenic in environmental and biological samples shows an increasing interest of many researchers in the subject. Because of the low level of arsenic species in real samples, many problems related with its speciation remain unresolved: species instability during sampling, storage and sample treatment, incomplete recovery of all species, matrix interferences, lack of appropriate certified reference materials and of sensitive analytical methods, etc. These aspects are underlined in this paper. The continued development of new analytical procedures pretending to solve some of these problems claim for an up-to-date knowledge of the recent publications. Therefore, this paper pretends to review the latest publications on the chemical speciation of arsenic, emphasizing the increasing activity in the development of accurate and precise analytical methods. In most of the cases, separation and preconcentration is necessary, followed by element-specific detection for sensitivity improvement. Hydride generation following separation procedures (e.g., ion-exchange or high performance liquid chromatography) coupled to atomic absorption or atomic emission detectors proved to have sufficient sensitivity to monitor arsenic exposure, although restricts the analysis to hydride-forming species. Modified procedures including some kind of heating in the presence of highly oxidizing agents have proved successful to completely decompose the arsenic containing compounds to arsenate and so to extend the range of compounds which can be determined by these methods. On-line arrangements have the additional advantage of avoiding excessive sample handling, although some of them involve numerous steps and others are too costly to be recommended for routine use. The analytical figures of merits, specially detection limits are given for most of the methods in order to afford comparison and judge possible applicability. These studies, which have been approached in many different ways, would lead to knowledge that are determinant in the understanding of the cycle of this element in environment and of its physiological and toxicological behavior in the living organisms.     

Electrochemical sensor for estriol hormone detection in biological and environmental samples

A stable conducting film for sensing using reduced graphene oxide (RGO), gold nanoparticles (GNPs), and potato starch (PS) is proposed. The characterization of the nanomaterials was obtained by ultraviolet and visible spectroscopy, dynamic light scattering, zeta potential, Fourier transform infrared spectroscopy, atomic force microscopy, and cyclic voltammetry. The voltammetric behavior of the RGO-GNPs-PS/GCE electrodes was studied in the presence of estriol and the results showed a high anodic peak current at 0.64 V. Under optimal conditions, an analytical curve was obtained, in which the anodic peak estriol was linear in the range from 1.5 to 22 μmol L^?1, with a detection limit of 0.48 μmol L^?1. The modified electrodes were applied for determination of estriol in environmental and biological samples. The proposed electrode was used for estriol determination in water and urine samples, which presented a recovery range from 92.1 to 106%, showing that RGO-GNPs-PS/GCE is a viable alternative for the detection of estriol and can be attractive for several electrochemical applications.     

Handling of environmental and biological samples via pre-column technologies

Sample handling is still a weak point in chromatography and in analytical chemistry in general. One consideration is the automation potential of new procedures. Solid-liquid extraction techniques in combination with pre-column technology are particularly promising in this regards. The construction and geometry of pre-columns both for conventional and narrow-bore HPLC are of major importance, since band broadening should be kept at a minimum for an optimal functioning of the analytical system. The various operations that can be carried out with such a pre-column are trace-enrichment, clean-up of the sample which depends on the type of adsorbents used in the precolumn, i.e., polar or apolar materials, ion exchangers or metal covered surfaces, etc., protection of the analytical column, field sampling and storage of samples and as a substrate for on-column chemical derivatizations. These various operations are demonstrated with practical examples from the fields of environmental and biological analysis. The selectivity can be further enhanced by coupling pre-column technology with selective detection models such as diode array UV, electrochemical or fluorescence detection. This enables the construction of optimal and integrated analysis systems which are fully automated and microprocessor controlled. They can also be made compatible with miniaturized LC-technology.     

Rapid determination of antimony in biological and environmental samples using instrumental neutron activation analysis

A rapid non-destructive activation analysis method has been developed for the determination of antimony. A high resolution low energy Ge detector is used to measure the 61.6 keV γ-ray from^122mSb (T=4.2 min). Sensitivities and detection limits for biological and environmental samples activated with thermal and epithermal neutrons are listed. The time required for the anlaysis is about 12 min per sample using thermal activation and 22 minutes using epithermal activation analysis.     

Determination of trace level mercury in biological and environmental samples by neutron activation analysis

Sorptivity studies with Chelex 100 column indicated chloride to be the best medium for the sorption of mercury. A radiochemical separation procedure has been developed for the determination of mercury by neutron activation analysis utilizing sorption of mercury on Chelex 100. The method was checked with Orchard Leaves and Tuna Fish standards from the National Institute of Standards and Technology.     

A system for the neutron activation analysis of trace elements in samples of biological and environmental interest

A neutron activation, ion exchange group separation and iterative least squares γ-ray spectroscopy method has been evaluated. This technique is suitable for multiple trace element analysis in a wide range of biological and environmental materials, since the major contaminants,²⁴Na,³²P, and⁴²K, are removed by an anion exchange resin and do not interfere with the analysis of the majority of the trace elements present. The iterative least squares method was tested with a mixture of standards. The reproducibility and accuracy varied from 3 to 26%. The larger uncertainties resulted from (1) the limited statistical accuracy associated with a low counting rate, and (2) bias introduced by the contaminants in the library of standard spectra even though radiochemical purity exceeded 99.8%. The rigorous least squares method can accurately compensate for instrumental drifts so that the sensitivity approaches the limit imposed by the statistical accuracy of the data and of the standard spectra. Minor components of the complex γ-spectrum were resolved and proved to be present at levels as low as 0.8% of the integral counting rate.     

Surface analysis of environmental samples

The surface chemical compositions of solid samples from environmental sources can differ from bulk or average compositions. The processes of adsorption, desorption, precipitation, dissolution, reaction etc., change the surface composition thereby affecting the surface chemistry. Accordingly, surface analytical information is important for the understanding of environmental chemistry involving solid surfaces. Analysis of environmental solid samples with their complex composition is a challenge to rapidly developing surface analytical techniques.     

Multi-element analysis of biological samples after intense neutron irradiation an fast chemical separation

For the simultaneous determination of many elements in small biological samples, a multi-element analysis has been developed using neutron activation. After a 24-hr irradiation in a neutron flux of 2.5·10¹⁴ n·cm⁻²·sec⁻¹ and after immediate chemical separation without cooling, it was possible to analyse 24 elements in bovine liver (NBS-SRM 1577). The separation apparatus, set up in a shielded cell can work four samples simultaneously, and its operation is fast enough to allow the detection of radioisotopes with a half-life of about 2 hrs (¹⁶⁵Dy,^57mSr,⁵⁶Mn). Amounts lower than 10⁻³ μg of Dy, Eu, Pr, Sm and Yb were determined.     

A green alternative method for analysis of ivermectin and moxidectin in environmental water samples using automatized preconcentration previous MEEKC

Antiparasitic drugs derived from macrocyclic lactones (MLs) are widely used in livestock activities around the world. An increasing concern for local authorities is the environmental pollution as a consequence of veterinary drugs widely used in rural areas. The purpose of environmental analysis is to monitor low levels of pollutant analytes in a large number of samples. Also, due to the lipophilic characteristic of these lactones, long‐chain solvents are usually required for performing sample treatment before and during the analysis. Therefore, sensitive, specific, robust, and environmentally friendly analytical methods are still required. In this paper, a new automatized preconcentration methodology followed by microemulsion electrokinetic chromatography analysis was developed for the simultaneous separation and determination of the most used MLs, ivermectin (IVM) and moxidectin (MXD) in environmental water. XAD‐4 resin was employed as an adsorbent for the preconcentration process and ethanol was used as the eluent. In contrast to traditional analysis for IVM and MXD, in this methodology nonpolluting solvents were involved during the whole process and therefore, it could be considered as a contribution to green analytical chemistry. Under optimal experimental conditions, LOD obtained for IVM and MXD were of 3 × 10^?3 and 3.6 × 10^?3 μg/L, respectively.     

Study of the chemical derivatization of zearalenone and its metabolites for gas chromatography-mass spectrometry analysis of environmental samples

This study compares different silylation procedures of zearalenone and its metabolites: alpha-zearalenol, beta-zearalenol, zearalanone, alpha-zearalanol and beta-zearalanol for gas chromatography-mass spectrometry (GC-MS) analysis. Four silylating agents among the most frequently used to derivatize polar organic compounds were tested: N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA), N-methyl-N-trimethylsilyltrifluoroacetamide (MSTFA), N,N-diethyltrimethylsilylamine (TMSDEA) and a commercial mixture of N,O-bis(trimethylsilyl)acetamide, trimethylchlorosilane and N-trimethylsilyimidazole. Previous studies showed that the addition of polar and/or basic solvents can significantly improve the yield of a reaction of derivatization. In this work, four solvents were tested: pyridine, dimethylformamide, acetonitrile and acetone. The influence of each solvent was studied as a function of the silylating agent/solvent ratio. The influences of the temperature and of the reaction time on the reaction yields were also evaluated. A GC-MS quantitation method associating methanol chemical ionization and selected ion storage with three ions was developed and successfully tested on a reconstituted sediment spiked in zearalenone and its metabolites.     

Comparative studies of methylmercury determination in biological and environmental samples

Some parameters affecting the accuracy of various approaches to methylmercury (MeHg) determination in biological and environmental samples were studied. Different isolation techniques (ion-exchange, extraction, volatilization, distillation) and final measurement via cold vapour atomic absorption spectroscopy (CV AA) or gas chromatography (GC) were compared. Results obtained by the various isolation techniques are comparable for almost all biological and environmental samples, except for soils and some sediments, where disagreement between the results obtained by GC and CV AA was found. In order to resolve these problems, a new separation technique based on distillation of MeHg from the sample followed either by CV AA or GC was developed. The new method results in very good recovery and reproducibility (95 ± 2%) for all samples examined (fish, mussel, shrimp, blood, hair, algae, sediment, etc.), is specific for MeHg and provides for its differentiation from other species by an indirect CV AA determination. Gas-chromatographic measurement of the isolated MeHg using different packings and conditioning of the columns is also discussed. The distillation method with GC detection is advantageous in producing cleaner chromatograms and in prolonging the life-time of the packing and the intervals between reconditioning.     

同位素稀释电感耦合等离子体质谱测定环境和生物样品中的镉

应用同位素稀释电感耦合等离子体质谱（ID—ICP—MS）对环境和生物样品茶叶、湖沉积物和人发标准物质中的镉进行测定研究。对电感耦合等离子体质谱（ICP—MS）的工作条件和参数进行了最优化。讨论了多原子离子和同量异位素对镉同位素比值的影响,通过天然镉标准溶液对质量歧视进行了校正,并优化同位素稀释剂的加入量。将该方法应用于茶叶、人发和沉积物标准物质的测定。