Elemental Speciation Analysis Research Articles

An overview of preconcentration techniques combined with inductively coupled plasma mass spectrometry for trace element determination in biological studies.

In the last decades, the determination of trace elements in biological materials has emerged as an important area of study because of its relevance to human health and the environment. Inductively coupled plasma mass spectrometry (ICP-MS) has proven to be a powerful tool for trace element analysis, owing to its high sensitivity and ability to determine several elements in a single measurement. However, given the complex nature of biological matrices and the presence of elements, most of them at ultratrace levels, it becomes crucial to complement ICP-MS with preconcentration techniques to increase the sensitivity and selectivity of analytical methods. This article presents an exhaustive overview of liquid- and solid-phase preconcentration techniques used in combination with ICP-MS for trace element determination in different biological samples from 2000 to the present. An in-depth discussion of the advances on the application of state-of-the-art solvents and materials in trace element extraction and preconcentration is presented. Special attention is given to different strategies for elemental speciation analysis, employing both chromatographic and non-chromatographic techniques. The role of automation in these methodologies is also described. Finally, future trends and challenges related to this topic are discussed.

Application of Hyphenated Technique in Element Speciation Analysis

Application of Hyphenated Technique in Element Speciation Analysis

Magnetic ion imprinting techniques for the separation and analysis of elemental speciation

Metal and metalloid elements have various possible isotopic compositions and oxidation states and often form coordination or covalent compounds with inorganic and organic small molecules or biological macromolecules, resulting in complex elemental speciation. Different species of the same element often have different properties, which dictate their behavior. Thus, elemental speciation analysis is vital for comprehensively and accurately assessing an element's environmental and biological effects and the corresponding risks. Because elemental speciation determines the behavior of an element in different environmental and biological processes, the analysis of elemental species has, in recent years, been important in various subjects, including analytical chemistry, environmental chemistry, geochemistry, ecology, agronomy, and biomedicine. The complexity of environmental and biological sample matrices, as well as the multiformity, low levels, and lability of chemical forms pose severe challenges in elemental speciation analysis. Therefore, the highly selective identification and efficient separation of native species is necessary for conducting the identification, quantification, ecotoxicity evaluation, and physiological function study of elemental speciation. Sample pretreatment by solid-phase extraction is an effective solution to the aforementioned problems, but the existing methods do not meet the requirements of current research. The transition of the target species from pre-processing to the detection device includes both on- and off-line arrangements. Compared with the on-line approach, the off-line approach requires more manual participation, increasing the analysis workload. However, the off-line approach can improve the analysis efficiency through high-throughput pretreatment when large batches of samples are encountered, meaning the off-line approach is still an effective model. Ion imprinting technology has been developed based on existing molecular imprinting technology, with four main steps present in the synthesis of ion imprinted polymers. First, ion imprinting technology uses metal ions as templates. Then, these templates are combined with the functional monomers through coordination, electrostatic or hydrogen bonding. The functional monomers simultaneously surround and fix the templates, after which the cross-linkers and functional monomers polymerize to prepare ion-imprinted polymers with a specific structure and composition. Finally, the imprinted holes are created in the polymers by eluting the template ions. Therefore, the template molecules, functional monomers, and cross-linkers are three precursors necessary for synthesizing ion-imprinted polymers. These polymers can specifically bind to the imprinted metal ions with accuracy, sensitivity, and reliability. In recent years, they have been widely used in separating, enriching, analyzing, and detecting elemental species. During solid-phase extraction, the non-magnetic adsorbent materials dispersed in the sample solution need to be separated by centrifugation or filtration, which is time-consuming and laborious. Because an external magnetic field can be used for rapid magnetic solid-phase extraction, it has become a potential method for separating and enriching elemental species. This review systematically summarizes the latest progress in ion-imprinting technology, including its principle and the preparation methods of ion-imprinted polymers. The challenges faced by ion imprinting technology are analyzed in the context of the development of ion-imprinting magnetic solid-phase extraction in elemental speciation analysis. Finally, the direction of future development and the strategies of ion imprinting technology in elemental speciation analysis are proposed. It is important to exploit novel organic-inorganic hybrid polymerization-based multifunctional ion-imprinted magnetic nanocomposites for the magnetic solid-phase extraction and separation of elemental species. By establishing the pretreatment protocols with high recognition selectivity, strong separation ability, large adsorption capacity, and good speciation stability, we expect to achieve the research objectives of simultaneously separating and enriching the multiple-species of typical metal/metalloid elements in environmental and biological samples.

Application of solid-phase microextraction in atomic spectrometry

With the growing requirements for the monitoring of heavy metals at an ultra-trace level in the environment and the real-time detection of toxic elements and their compounds for environmental pollution accidents, researchers devoted significant efforts to seeking atomic spectrometric methods that can be used for the simple, low cost, rapid, and field usable detection of targeted elements and their pollutants. Although conventional atomic spectrometric methods can easily realize the routine analysis of toxic elements in various samples in the laboratory, their bulky instruments and the complex sample matrix of environmental samples limit their further applications in field environmental analysis and complex sample analysis. Solid-phase microextraction (SPME) is an environmentally-friendly sample pre-treatment technique, which can significantly simplify sample pretreatment, increase sensitivity, and reduce the interference from the sample matrix, thus being one of the most ideal sampling techniques for the detection of ultra-trace toxic elements and their compounds by atomic spectrometry (AS) with high sensitivity and good selectivity. During the past decades, significant developments of SPME-AS including novel coating nanomaterials, desorption mode, miniaturized spectrometer, and its use for field elemental analysis have been made to improve the analytical performance in the detection of toxic elements and their pollutants. Herein, we present a short review concerning recent advances in elemental analysis by SPME-AS. Particularly, we highlight their application in the field of environmental analysis based on combing SPME with the available microplasma-based atomic spectrometer. The conclusion section addresses the current challenges and gives an outlook on potential future trends in the field of elemental analysis and elemental speciation analysis.

Flow-Injection Methods in Water Analysis-Recent Developments.

Widespread demand for the analysis and control of water quality and supply for human activity and ecosystem sustainability has necessitated the continuous improvement of water analysis methods in terms of their reliability, efficiency, and costs. To satisfy these requirements, flow-injection analysis using different detection methods has successfully been developed in recent decades. This review, based on about 100 original research papers, presents the achievements in this field over the past ten years. Various methodologies for establishing flow-injection measurements are reviewed, together with microfluidics and portable systems. The developed applications mostly concern not only the determination of inorganic analytes but also the speciation analysis of different elements, and the determination of several total indices of water quality. Examples of the determination of organic residues (e.g., pesticides, phenolic compounds, and surfactants) in natural surface waters, seawater, groundwater, and drinking water have also been identified. Usually, changes in the format of manual procedures for flow-injection determination results in the improvement of various operational parameters, such as the limits of detection, the sampling rate, or selectivity in different matrices.

Elemental Speciation Analysis in Environmental Studies: Latest Trends and Ecological Impact.

Speciation analysis is a key aspect of modern analytical chemistry, as the toxicity, environmental mobility, and bioavailability of elemental analytes are known to depend strongly on an element’s chemical species. Henceforth, great efforts have been made in recent years to develop methods that allow not only the determination of elements as a whole, but also each of its separate species. Environmental analytical chemistry has not ignored this trend, and this review aims to summarize the latest methods and techniques developed with this purpose. From the perspective of each relevant element and highlighting the importance of their speciation analysis, different sample treatment methods are introduced and described, with the spotlight on the use of modern nanomaterials and novel solvents in solid phase and liquid-liquid microextractions. In addition, an in-depth discussion of instrumental techniques aimed both at the separation and quantification of metal and metalloid species is presented, ranging from chromatographic separations to electro-chemical speciation analysis. Special emphasis is made throughout this work on the greenness of these developments, considering their alignment with the precepts of the Green Chemistry concept and critically reviewing their environmental impact.

Three-Dimensional Printed Dual-Mode Chemical Vapor Generation Point Discharge Optical Emission Spectrometer for Field Speciation Analyses of Mercury and Inorganic Selenium.

Due to the large size and high energy consumption of instruments, field elemental speciation analysis is still challenging so far. In this work, a portable and compact system device (230 mm length × 38 mm width × 84 mm height) was fabricated by using three-dimensional (3D) printing technology for the field speciation analyses of mercury and inorganic selenium. The device comprises a cold vapor generator, photochemical vapor generator, and miniaturized point discharge optical emission spectrometer (μPD-OES). For mercury, inorganic mercury (IHg) was selectively reduced to Hg0 by cold vapor generation, whereas the reductions of both IHg and methylmercury (MeHg) were obtained by photochemical vapor generation (PVG) in the presence of formic acid. For selenium, Se(IV) and total inorganic selenium were converted to their volatile species by PVG in the presence and the absence of nano-TiO2, respectively. The generated volatile species were consequently detected by μPD-OES. Limits of detection of MeHg, IHg, Se(IV), and Se(VI) were 0.1, 0.1, 5.2, and 3.5 μg L-1, respectively. Precision expressed as the relative standard deviations (n = 11) were better than 4.5%. The accuracy and practicality of the proposed method were evaluated by the analyses of Certified Reference Materials (DORM-4, DOLT-5, and GBW(E)080395) and several environmental water samples with satisfactory recoveries (95-103%). This work confirms that 3D printing has great potential to fabricate a simple, miniaturized, easy-to-operate, and low gas and power consuming atomic spectrometer for field elemental speciation analysis.

Ozone Chemistry and Photochemistry at the Surface of Icelandic Volcanic Dust: Insights from Elemental Speciation Analysis

Ozone Chemistry and Photochemistry at the Surface of Icelandic Volcanic Dust: Insights from Elemental Speciation Analysis

A hydrothermal apparatus for x-ray absorption spectroscopy of hydrothermal fluids at DESY.

We present a new autoclave that enables in situ characterization of hydrothermal fluids at high pressures and high temperatures at synchrotron x-ray radiation sources. The autoclave has been specifically designed to enable x-ray absorption spectroscopy in fluids with applications to mineral solubility and element speciation analysis in hydrothermal fluids in complex compositions. However, other applications, such as Raman spectroscopy, in high-pressure fluids are also possible with the autoclave. First experiments were run at pressures between 100 and 600 bars and at temperatures between 25 °C and 550 °C, and preliminary results on scheelite dissolution in fluids of different compositions show that the autoclave is well suited to study the behavior of ore-forming metals at P-T conditions relevant to the Earth's crust.

Analytical Methodologies for Agrometallomics: A Critical Review.

Agrometallomics, as an independent interdiscipline, is first defined and described in this review. Metallic elements widely exist in agricultural plants, animals and edible fungi, seed, fertilizer, pesticide, feedstuff, as well as the agricultural environment and ecology, and even functional and pathogenic microorganisms. So, the agrometallome plays a vital role in molecular and organismic mechanisms like environmetallomics, metabolomics, proteomics, lipidomics, glycomics, immunomics, genomics, etc. To further reveal the inner and mutual mechanism of the agrometallome, comprehensive and systematic methodologies for the analysis of beneficial and toxic metals are indispensable to investigate elemental existence, concentration, distribution, speciation, and forms in agricultural lives and media. Based on agrometallomics, this review summarizes and discusses the advanced technical progress and future perspectives of metallic analytical approaches, which are categorized into ultrasensitive and high-throughput analysis, elemental speciation and state analysis, and spatial- and microanalysis. Furthermore, the progress of agrometallomic innovativeness greatly depends on the innovative development of modern metallic analysis approaches including, but not limited to, high sensitivity, elemental coverage, and anti-interference; high-resolution isotopic analysis; solid sampling and nondestructive analysis; metal chemical species and metal forms, associated molecular clusters, and macromolecular complexes analysis; and metal-related particles or metal within the microsize and even single cell or subcellular analysis.

Exploring bufferless iron speciation in seawater by Competitive Ligand Equilibration-Cathodic Stripping Voltammetry: Does pH control really matter?

Iron speciation in seawater is of the utmost importance as this element plays a central role in the regulation of primary productivity. Here we present the development of a CLE-CSV (Competitive Ligand Equilibration-Cathodic Stripping Voltammetry) procedure for iron speciation in seawater avoiding for the first time the use of the pH buffer (2,3-dihydroxynaphthalene is used as the added ligand, atmospheric oxygen as the catalytic enhancer and a 1 mL volume per sample aliquot). The unbuffered method was setup, validated by using known ligands and finally applied to the analysis of six seawater samples from the Ross Sea (Antarctica). The validation procedure demonstrated that ultratrace levels of ligands may be reliably determined and the application to seawater samples proved that the complex natural ligand pool can be detected with results undistinguishable from the ones obtained by the buffered procedure. The proposed method demonstrated a new principle in trace element speciation analysis by CLE-CSV, namely that the equilibration step may be performed at natural pH, whereas the pH may be set at its optimal value for sensitivity during analysis, thanks to the raise in pH at the electrode/solution interface caused by oxygen reduction. This change in paradigm paves the way to the investigation of iron speciation at natural pH in traditionally difficult samples that show circumneutral or slightly acidic pH values. The relevance of the here proposed approach to existing speciation procedures by CLE-CSV is also discussed.

The migration dynamics and the speciation of arsenic in the Hetao area, Inner Mongolia.

Arsenic contamination of the groundwater in the Hetao area in Inner Mongolia, China, has been a serious problem since the 1980s. In this study, the behavioral mechanics of arsenic in soil in the Hetao area, in relation to arsenic concentrations in groundwater, were studied using elemental speciation analysis. It is for probing the possible mechanisms of correlation and interaction within water and soil of the area, which is little work on it not only in the Hetao area but also worldwide. Associated with our previous work on water in this area, soil samples were collected along transects through areas strongly affected by arsenic poisoning. Sequential extractions were used to determine the speciation in soil of arsenic and other elements (Cd, Cu, Mo, Pb, Sb, Sn, and Zn) which are with similar geochemical behaviors to arsenic in natural systems. The results show that the arsenic concentration in soil is correlated with arsenic concentration in groundwater. This implies that arsenic transformation as a main factor of the resident poisoning of the area could be related with groundwater and soil. These results suggest that arsenic poisoning in the Hetao area is related with water and soil. The tracers moving through water are retained in the shallow stratum including soil and persist in the water affected by the movement of arsenic through the shallow stratum and soil. Graphical abstract.

A retrospective and prospective of the use of bio- and nanomaterials for preconcentration, speciation, and determination of trace elements: a review spanning 25years of research.

This review covers the investigations carried out with my colleagues and students during the last 25years aimed at the development of analytical procedures for the preconcentration and/or speciation analysis of trace and ultra-trace elements using bio- and nanosorbents employing different methodologies, analytical techniques, and instrumental approaches. In the last years, an important part of this research was based on the use of nanomaterials for preconcentration and/or speciation studies. For their properties, they constitute a break point in the evolution of analytical chemistry. Special attention was paid to carbon nanotubes (CNTs) that resulted effective sorbents in flow systems using different immobilization strategies to improve their sorption capabilities. They resulted unique tools for on-line solid-phase (micro)extraction methods providing the appropriate selectivity (clean-up) and sensitivity (preconcentration) to reach the expected levels of many elements in matrices of biological or environmental interest. The performance of the different substrates, their strengths and weaknesses for the determination of trace elements, and their species in different matrices by a variety of analytical techniques are discussed in detail, along with perspectives and possible challenges in future development. This survey contains 96 references and covers primarily the literature published over the last 25years by our research group. Relevant publications on the topics discussed were also included.

Introducing Frontal Chromatography-Inductively Coupled Plasma-Mass Spectrometry as a Fast Method for Speciation Analysis: The Case of Inorganic Arsenic.

A frontal chromatography-ICP-MS method (FC-ICP-MS) is proposed as an innovative approach for fast elemental speciation analysis: inorganic arsenic speciation was selected as the first case study to prove the feasibility of the technique and to explore its potentialities and limits. The principal benefits of the FC-ICP-MS approach are the short analysis time and the very simple instrumental setup. As(III) and As(V) front separation is performed over a strong anion exchanger at pH 7.5. After the optimization of the instrumental setup and the frontal chromatographic parameters, As(III) and As(V) concentrations up to 240 μg/kg can be determined within 120-140 s using different univariate and multivariate calibration approaches. Best results in terms of accuracy in prediction were obtained using the partial least squares (PLS) calibration achieving limits of detection of 0.18 and 0.21 μg/kg for As(III) and As(V), respectively. This approach was also used to establish the figures of merit of the method. The proved feasibility and good performances (in terms of analysis time and accuracy) of this technique lay the groundwork for future applications of FC-ICP-MS for the speciation of other elements.

Determination of arsenic speciation in 17 commonly used traditional Chinese herbal medicines by HPLC-ICP-MS

The element speciation analysis for heavy metals in herbal medicines is still in the beginning stage. In this study,the total amount of arsenic( As) in 103 batches of 17 commonly used Chinese medicines( including 16 plant medicines and 1 medicinal fungus) was detected by inductively coupled plasma mass spectrometry( ICP-MS). Furthermore,based on HPLC-ICP-MS,the simultaneous detection methods of six As speciation kinds in traditional Chinese medicines were established. An AS7 anion exchange column was selected and the As forms in 17 traditional Chinese medicines was systematically analyzed. The results showed that the method of pretreatment of medicinal materials by microwave digestion and the detection of total amount of As by ICP-MS was stable and reliable. As for the speciation analysis of As,the high-speed ultrasonic extraction method was adopted,and it showed that the linear relationship of the six As speciation was satisfied with the correlation coefficient R2>0. 999 9. The LOQ of six kinds of As speciation were 0. 20,0. 10,0. 15,0. 10,0. 25,0. 10 μg·L~(-1) for arsenic betaine( As B),arsenious acid [As( Ⅲ) ],dimethyl arsenic( DMA),arsenic choline( As C),monomethyl arsenic( MMA),arsenic acid[As( Ⅴ) ],respectively. The recoveries were between 84. 24% and 121. 5%,and the relative standard deviations were 2. 7% to 11%. Among the 103 batches of medicinal materials,only one batch of sample As exceeded the Chinese Pharmacopoeia limit standard; As( Ⅲ) and As( Ⅴ) had high detection rate in 103 batches of Chinese herbal medicines,within which As( Ⅴ) was the main detected form,and inorganic As accounted for the ratio reached 80. 90%-98. 73%; some samples detected DMA,MMA and As B,As C was not detected in any batch. This study established an analytical method suitable for the speciation of As in Chinese herbal medicines,and provided basic data for As residual residue in Chinese herbal medicines,which can provide important reference for the risk assessment and quality standards.

Speciation of trace elements in groundwater, surface water and sediments: a short review

In order to understand the interaction between groundwater, surface water and sediments, there is a need for speciation analysis of trace elements in the mentioned matrices. This could be done experimentally or by calculation with e.g. thermodynamic codes. This article will give a short overview of methods with some examples and results. Speciation in water could be determined by thermodynamic calculations with e.g. PHREEQC or Visual MINTEQ. Experimental speciation in water could be done by ultrafiltration or dialysis in situ. If applicable, in situ dialysis in the field is simple with little need of equipment. Speciation of trace elements in drinking water is of special interest to assess possible health effects. Speciation of trace elements in sediments and soils can be done by any one of the numerous selective extractions. Which speciation approach depends on which trace elements are of interest. A common need is to get information about plant uptake of specific elements.

Current Elemental Speciation Analysis from a Green Chemistry Perspective

Current Elemental Speciation Analysis from a Green Chemistry Perspective

Elemental Speciation Analysis of Iron Compounds in Carbonized Biomass and Its Thermal Behavior by Oxidation Reaction

Elemental Speciation Analysis of Iron Compounds in Carbonized Biomass and Its Thermal Behavior by Oxidation Reaction

Sources of indoor air pollution at a New Zealand urban primary school; a case study

Children are particularly vulnerable to the health effects of air pollution and as they spend a large proportion of time at school, this is an important environment for children's exposure to air pollution. Understanding the factors that influence indoor air quality in schools is critical for the assessment and control of indoor air pollution. This study analysed the concentration and sources of air pollution at an urban primary school (5–11 years) in Wellington, the capital of New Zealand. Over a three-week period during spring, indoor measures of particulate matter (PM2.5, PM10), temperature, humidity, carbon dioxide (CO2) and nitrogen dioxide (NO2) were taken and hourly air particulate matter samples (PM2.5, PM10-2.5) were collected inside and outside for elemental speciation analysis. Indoor PM10 concentrations during the school day were significantly (p < 0.001) higher than outdoor concentrations 30.1 (range 10.0–75.0, SD 1.9) μg m−3 c.f. 8.9 (range <1.0–35.0, SD 6.8) μg m−3. Elemental analysis and receptor modelling of PM samples showed that indoor PM10 was primarily composed of crustal matter (soil) elements, possibly brought in on children's footwear. The primary driver of indoor PM2.5 was from the infiltration of outdoor pollutants inside, with by-products of motor vehicle emissions the main contributor to indoor PM2.5. There is a need for mitigation strategies to reduce exposure to indoor air pollution at school, such as improved cleaning methods, reducing the use of carpet in schools and improved ventilation. The findings from this study will be applicable to many other schools and public buildings with high foot traffic.

Graphene oxide as a stationary phase for speciation of inorganic and organic species of mercury, arsenic and selenium using HPLC with ICP-MS detection.

This work demonstrates the power of graphene and graphene oxide (GO) as stationary phases for high performance liquid chromatography (HPLC) based elemental speciation analysis combined with detection by inductively coupled plasma mass spectrometry (ICP-MS). Inorganic mercuric and organomercuric compounds coordinate with 2-thiosalicylic acid (TSA) to form Hg-TSA complexes. These complexes are retained by GO owing to its strong π electron stacking capability for TSA. Separation of the four mercury species tested was achieved within 12min with resolutions of 1.8-3.4. Similarly, inorganic anionic species of arsenic and selenium, and organoarsenicals are electrostatically attracted by aromatic quaternary ammonium cations in the mobile phases. Organoarsenicals also can be separated by using long alkyl quaternary ammonium compounds. Aromatic quaternary ammonium compounds possess particularly high affinity to GO because of strong π interaction. This leads to effective retention of the As/Se anions. A comparison between graphene and GO as stationary phases for HPLC separation of mercury and arsenic species demonstrates negligible difference. Arsenic species are separated within 32min, and selenium species are achieved within 20min. The mobile phase also allows efficient separation of iodate, iodide, bromate, bromide, chromic acid and chromate. Analysis of a certified fish tissue by HPLC-ICP-MS using the GO@SiO2 column demonstrates its feasibility for routine elemental analysis. Good agreement is found between experimental results and certified values, with recoveries ranging between 92 and 96%. Graphical abstract Graphene oxide as a stationary phase for high performance liquid chromatography with inductively coupled plasma mass spectrometric detection (HPLC-ICP-MS) in speciation analyses of mercury, arsenic, selenium, iodine, bromine and chromium is achieved for the first time.