Combination of three analytical techniques for speciation of Al in environmental samples

An analytical scheme is proposed which combines three speciation techniques for determination of particular Al species in soil extracts and percolating waters. A cation-exchange fast protein liquid chromatography — inductively coupled plasma atomic emission spectrometry (FPLC-ICP-AES) procedure, a microcolumn chelating ion-exchange chromatography- atomic absorption spectrometry (MCC-ETAAS) technique and the 8-hydroxyquinoline spectrophotometric method (8HQ-spectrophotometry) were employed. The FPLC-ICP-AES procedure offers determination of Al³⁺ (retention time 4.5 min) and Al(OH)²⁺ species (retention time 4.0 min) which are separated from Al(OH)⁺ ₂ (retention time 1.5min). AlF²⁺ coelutes with Al(OH)²⁺ species, while Al(SO₄)⁺, AlF⁺ ₂ and negatively charged Al organic complexes coelute with Al(OH)⁺ ₂ species. The MCC-ETAAS technique enables determination of the sum of positively charged monomeric aqua- and hydroxy-Al species plus sulphate- and fluoro-Al complexes. Employing the 8HQ-spectrophotometry the sum of positively charged monomeric aqua- and hydroxy-Al species plus sulphato- and most of the labile organic Al species are determined. The sensitivities of these selected techniques were adequate for speciation of Al in the samples analyzed. On the basis of the specific selectivity of a particular technique various groups of Al species may be determined. Thus, the comparison of analytical data from complementary procedures provides more comprehensive information on Al species present in soil extracts and percolating waters.     

Inorganic and methylmercury speciation in environmental samples

The different strategies for mercury species analysis in environmentally-related samples are reviewed. After consideration of the main different steps involved in the speciation of mercury, such steps are discussed with more extension for mercuric ion and methylmercury. The different approaches for preservation of these mercury species during the storage of samples are considered. Different ways for the extraction of mercury species from the several possible environmental compartments and the possibilities for preconcentration of such species after previous derivatization reactions are discussed. Mercuric ions and methylmercury chromatographic and non-chromatographic separations along with different techniques used for sensitive and selective detection of mercury are also critically reviewed. Ranges of published detection limits achievable for such species determination, by using hyphenated techniques between a chromatographic separation and a specific atomic detector are also given.     

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.     

Aluminium speciation in environmental samples: a review

Because of its toxic effects on living beings, Al may represent an environmental hazard, particularly under increased acidic conditions. Growing environmental concern over the presence of increased Al concentrations in soil solutions and fresh waters resulted in the development of numerous analytical techniques for the determination of Al species. Al has a very complex chemistry that is significantly influenced by pH. Different Al species are present in environmental solutions, and many of them are unstable. Contamination of samples and reagents by extraneous Al represents an additional problem in speciation of Al at trace concentrations. Due to these reasons quantitative determination of particular chemical forms of Al is still a very difficult task for analytical chemists. The most important analytical methodologies of the last decade and new trends for the speciation of Al in environmental samples are comprehensively reviewed here.     

Organolead speciation in environmental samples: a review

The speciation of organolead in some environmental samples is reviewed. Sampling, storage and pretreatment methods for water, soil, sediment and air samples are discussed before an assessment of recent developments in analytical methods.     

Coupling techniques in speciation analysis

Summary Direct coupling techniques in speciation analysis lead to reproducible results with lower risks of trace contamination or losses of analytes in a shorter period of time. The direct coupling mode seems to be most promising for liquid chromatographic separation methods — especially gel permeation chromatography — and for some electrophoretic methods — as flow-through and capillary techniques. Promising detection methods are Flame-AAS and ICP-OES but also hydride-generation AAS and chemical reaction detectors in continuous-flow technique.     

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.     

Recent developments in speciation and determination of organometallic compounds in environmental samples

Summary Recent developments in the techniques of speciation and determination of organometallic compounds in the environment are reviewed. There is an increasing trend in the use of high performance liquid chromatography as separation tool, and in the use of plasma-excited atomic emission spectrometry as detector. New techniques have been reported to overcome the historically difficult interface of HPLC to furnace AAS. There are also new techniques in the derivatization of ionic organometallic species for gas chromatography. Tandem analytical systems are getting more and more sophisticated, so are the sensitivity and specificity.     

Biochemical speciation analysis by hyphenated techniques

The elucidation of mechanisms that govern the essentiality and toxicity of trace elements in living organisms is critically dependent upon the possibility of the identification, characterization and determination of chemical forms of these elements involved in life processes. The recent progress and the state-of-the-art of biochemical species-selective trace element analysis are critically evaluated with particular emphasis on the use of techniques combining the high selectivity of high performance liquid chromatography (HPLC) with the elemental or molecular specificity of mass spectrometry [using inductively coupled plasma (ICP) or electrospray ionization (ESI)]. The potential and limitations of hyphenated techniques as a tool for speciation of metals and metalloids in biological materials is discussed using a number of examples drawn from the latest research in the authors’ laboratory.     

Simultaneous speciation analysis of inorganic nitrogen with the use of ion chromatography in highly salinated environmental samples

We present the development of a method for the simultaneous determination of inorganic nitrogen species in oxidized (NO₂^–, NO₃^–) and reduced (NH₄⁺) forms using ion chromatography with diode‐array detection (205, 208, and 425 nm, respectively). The oxidized forms were determined directly after the separation in the anion exchanger, while the reduced form was determined in the column hold‐up time after derivatization with the Nessler reagent. The use of an appropriate modifier (Seignette reagent) and mobile phase (NaCl) enabled the determination of inorganic nitrogen species in highly salinated environmental samples (water, sediments). Moreover, low detection limits were obtained of 0.04 mg/L for NH₄⁺ and 0.006 and 0.005 mg/L for NO₂^– and NO₃^–, respectively. The analysis of environmental samples indicated NH₄⁺ contents of up to 1161 ± 47 mg/kg and NO₃^– of up to 148 ± 6 mg/kg for sediment samples, as well as the NH₄⁺ concentrations of up to 0.98 ± 0.10 mg/L, NO₂^– of up to 24 ± 1 mg/L and NO₃^– of up to 20 ± 1 mg/L for water samples.     

Alteration of biological samples in speciation analysis of metalloproteins

For investigations of metalloproteins by speciation analysis, the integrity of the protein–metal complexes before and during separation is crucial. Knowledge about potential alterations of the samples is thus essential to avoid misinterpretations of the analytical results. Chromatographic element profiles of different cytosolic samples from animal tissues were measured repeatedly to estimate the sample stability. The dependence of the signals on the dwell time of the sample in an autosampling device at 4 °C for a period of 10 h was observed. Alterations in the element content of different metal-containing fractions were quantified by means of recovery values. Some metalloprotein fractions (e.g. ≈27-kDa arsenic, ≈27-kDa iron and different zinc fractions) were stable or only minor alterations were observed and for their investigation an autosampling device is therefore suitable. However, most of the other metalloprotein fractions, especially nickel-containing proteins, showed major alterations: these samples should therefore be analysed immediately after preparation or directly after thawing. Figure Chromatographic manganese-profiles of 11 repeated SEC-ICP-MS-separations of rat brain cytosol. The first sample at time 0 h was the run immediately started after thawing of the prepared cytosol; the other samples were measured hourly, taken from the same sample vial. In addition to the time axis the estimated molecular mass axis is plotted Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Gas chromatography--inductively coupled plasma--time-of-flight mass spectrometry for the speciation analysis of organolead compounds in environmental water samples

The application of inductively coupled plasma--time-of-flight mass spectrometry for the speciation analysis of organolead compounds in environmental waters is described. Construction of the transfer line was achieved by means of a relatively simple and rapid coupling procedure. Derivatization of the ionic lead species was achieved by in-situ propylation with sodium tetrapropylborate; simultaneous extraction of the derivatized compounds in hexane was followed by separation and detection by capillary gas chromatography hyphenated to inductively coupled plasma-time-of-flight mass spectrometry. Detection limits for the different organolead species ranged from 10 to 15 fg (as Pb), corresponding to procedural detection limits between 50 and 75 ng L(-1), on the basis of a 50 mL snow sample, extraction with 200 microL hexane, and subsequent injection of 1 microL of the organic extract on to the column. The accuracy of the system was confirmed by additional analysis of the water samples by capillary gas chromatography coupled with microwave-induced plasma-atomic-emission spectrometry and the analysis of a standard reference material CRM 605 (road dust) with a certified content of trimethyllead.     

Separation techniques in speciation analysis for organometallic species

A comprehensive review of the state-of-the-art of the separation of various organically-bound metals and metalloids for speciation analysis is presented. Recent developments in chromatographic (gas, liquid and supercritical fluid), electrophoretic (free-flow and gel) and fractionation techniques are discussed, followed by a survey of pertinent applications to speciation analysis for organometals and metalloids. The required sample characteristics for a given separation technique are specified and appropriate derivatization procedures are characterized. Methods applicable to the speciation of organic species of a particular element in various matrices are critically evaluated.List of abbreviations APS ammonium pentanesulfonate - CCC counter current chromatography - CZE capillary zone electrophoresis - DBT dibutyltin - DCyT dicyclohexyltin - DDTC diethyldithicarbamate - DEAE diethylaminoethyl gel (anion exchanger) - DEL diethyllead - DET diethyltin - DMA dimethylarsinic acid - DMGe dimethylgermanium - DMHg dimethylmercury - DML dimethyllead - DMSb dimethylstibinic acid - DMT dimethyltin - DPhT diphenyltin - DPrT dipropyltin - EDTA ethylenediaminetetraacetate - FFF field flow fractionation - GC gas chromatography - HEPES 4-(2-hydroxyethyl)-1-piperazine-ethanesulfonic acid - HPLC high performance liquid chromatography - ICP inductively coupled plasma - IEC ion exchange chromatography - IIC ion interaction chromatography - LC liquid chromatography - MBT monobutyltin - MCyT monocyclohexyltin - MEA monoethylarsinic acid - MEHg monoethylmercury - MEL monoethyllead - MET monoethyltin - MIP microwave induced plasma - MMA monomethylarsonic acid - MMGe monomethylgermanium - MMHg monomethylmercury - MML monomethyllead - MMSb monomethylstibonic acid - MMT monomethyltin - MPhHg monophenylmercury - MPhT monophenyltin - MPrT monopropyltin - MS mass spectrometry - NAA neutron activation analysis - NaBS sodium 1-butanesulfonate - NaDS sodium dodecylsulfonate - NaPS sodium pentanesulfonate - PAGE polyacrylamide gel electrophoresis - PAR 4-(2-pyridylazo)resorcinol - PIXE proton induced X-ray emission - QF quartz furnace - RPC reversed phase partition chromatography - SDS sodium dodecyl sulfate - SEC size exclusion chromatography - SFC supercritical fluid chromatography - TBAP tetrabutylammonium phosphate - TAL tetraalkyllead - TBT tributyltin - TCyT tricyclohexyltin - TeEL tetraethyllead - TEL triethyllead - TeML tetramethyllead - TET triethyltin - TGME thioglycolic methyl ester - THF tetrahydrofuran - TMA trimethylarsinic acid - TMAH tetramethylammonium hydroxide - TMGe trimethylgermanium - TML trimethyllead - TMT trimethyltin - TPhT triphenyltin - TPrT tripropyltin - Tris tris(hydroxymethyl)aminomethane     

Liquid chromatography-hydride generation-atomic fluorescence spectrometry hybridation for antimony speciation in environmental samples

Atomic fluorescence spectrometry was used as an element-specific detector in hybridation with liquid chromatography (LC) and hydride generation for the speciation of Sb(III), Sb(V) and trimethylantimony dichloride (TMSbCl₂). The three species were poorly resolved in a single chromatogram but good results were obtained by anion-exchange chromatography, using a mobile phase with 20 mM EDTA and 8 mM hydrogenphthalate to separate Sb(III) and Sb(V) and 1 mM carbonate at pH 10 to separate Sb(V) and TMSbCl₂. Calibration graphs were linear between 2 and 100 μg l⁻¹. Detection limits were 0.9, 0.5 and 0.7 μg l⁻¹ for Sb(III), Sb(V) and TMSbCl₂, respectively. The method was applied to the speciation of antimony in environmental samples.     

Factors affecting arsenic speciation in environmental samples: sample drying and storage

Arsenic is a ubiquitous element. Its toxicity, mobility, and bioaccumulation depend usually on its chemical form, and therefore, arsenic speciation is indispensable for the assessment of environmental risk and human hazard. Little is known about the effect of sample preparation procedures, such as drying and storage, on the resulting arsenic speciation. In this study, we investigated the influence of different drying methods and storage conditions on the arsenic speciation in mineral soils, organic soils, and plants. Drying soils and plants using different methods may change the concentrations of the total methanol–water (20%,?v/v) extractable arsenic, the proportion of organic arsenic and the ratio of arsenite-to-arsenate. Loss of methanol–water extractable arsenic compounds (up to 63%) was observed particularly in the samples rich in water. Following drying, the speciation of organic arsenic changed less than that of inorganic arsenic. Drying showed little influence on the total arsenic determination. None of the storage methods tested could preserve the arsenic speciation in organic soils and plants, although arsenic speciation after one-month storage varied less in freeze-dried samples than wet samples. Storage of the samples at low temperatures (2 or??20°C) had the largest impact on the samples rich in organic matters, leading to less arsenic being extractable by methanol–water. Both drying and storage of the soil and plant samples changed apparently the arsenic speciation. Therefore, we recommend conducting the arsenic speciation possibly with fresh and wet samples, so that the results of arsenic speciation may be more approaching the original states.     

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.     

A review on speciation of iodine-129 in the environmental and biological samples

As a long-lived beta-emitting radioisotope of iodine, ¹²⁹I is produced both naturally and as a result of human nuclear activities. At present time, the main part of ¹²⁹I in the environment originates from the human nuclear activity, especially the releases from the spent nuclear fuel reprocessing plants, the ¹²⁹I/¹²⁷I ratios have being reached to values of 10⁻¹⁰ to 10⁻⁴ in the environment from 10⁻¹² in the pre-nuclear era. In this article, we review the occurrence, sources, inventory, and concentration level of ¹²⁹I in environment and the method for speciation analysis of ¹²⁹I in the environment. Measurement techniques for the determination of ¹²⁹I are presented and compared. An overview of applications of ¹²⁹I speciation in various scientific disciplines such as radiation protection, waste depository, and environmental sciences is given. In addition, the bioavailability and radiation toxicity (dose to thyroid) of ¹²⁹I are discussed.     

A comparison between ICP-MS and AFS detection for arsenic speciation in environmental samples

Performances of two atomic detectors, Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) and Atomic Fluorescence Spectrometry (AFS) have been compared for arsenic speciation in environmental samples. Instrumental couplings, based on the use of high performance liquid chromatography (HPLC), hydride generation (HG), and the two atomic detectors were used for the speciation of arsenite, arsenate, dimethylarsinic acid and monomethylarsonic acid. Optionally, arsenobetaine was also determined using on-line ultraviolet (UV) photooxidation. The detection limits ranging from 0.1 to 0.3 mug l(-1) (as As) and the precision >10% RSD obtained with HPLC-(UV)-HG-AFS were comparable with those obtained with HPLC-(UV)-HG-ICP-MS. Both instrumental coupling were applied to the NRCC-TORT-1 and several environmental samples, such as seawater, freshwater, sediments, bivalves and bird eggs, taken from two areas with different degrees of pollution. No influence of the sample matrix was observed on the results using external calibration and standard additions methods, for both coupled techniques.     

Activation analysis of mercury in environmental samples

Neutron-activation analysis has been applied to the determination of mercury in a variety of environmental samples (Table 11) and so far has played an important role in the environmental research concerned with mercury pollution. The virtues of this method as its high sensitivity, applicability to various samples make the method attractive. On the other hand the high cost, limited availability of irradiation facilities, the time consumming analysis (due to irradiation and cooling) are important drawbacks and limit the use of the method, particularly in routine work. With the development of flameless atomic absorption mercury determination is more and more carried out with the aid of the latter technique. It seems, however, that activation analysis will remain a reference method and an anchorage in the cases when other methods fail.