Experimental design optimisation and validation by accuracy profile of a novel method for Hg speciation analysis by HPLC-ICP-MS and application to Total Diet Studies.

This study addresses the development and validation of an analytical method for speciation analysis of mercury (inorganic/Hg2+ and methylmercury/CH3Hg+) in fishery products. The Hg species are separated by reversed-phase (RP) high-performance liquid chromatography (HPLC) coupled to inductively coupled plasma mass spectrometry (ICP-MS). The effective separation of Hg2+ and CH3Hg+ was achieved in <8 min using a peptide mapping RP column and a mobile phase containing 2-mercaptoethanol at 0.25% (v/v) and methanol at 1% (v/v). The optimization was carried out using an experimental design through response surface methodology (RSM) with central composite design (CCD), addressing both the HPLC separation and the sample extraction. The method validation was carried out based on the accuracy profile approach. For this purpose, six series of measurements were carried out in duplicate over a time span of 2 months. The limits of quantification (LOQ) were 2.5 µg/kg (wet weight, ww) for CH3Hg+ and 1.2 µg/kg (ww) for Hg2+. The intermediate reproducibility in terms of coefficient of variation (CVR) was <6%. The bias (%) obtained for the analysis of four certified reference materials (CRMs), namely TORT-3 (lobster hepatopancreas), SRM 1566-b (oyster tissue), SQID-1 (cuttlefish) and NMIJ CRM 7402-a (cod fish tissue) was <7%. This demonstrates the method robustness and suitability for routine speciation analysis of CH3Hg+ and Hg2+ in fishery products. The method is intended to be applied for the analysis of the panel of fishery products and fish-based foods in the framework of the (ongoing) third French Total Diet Study.

Simultaneous microwave digestion for total arsenic and inorganic arsenic in local shrimp and prawn commodities of Brunei Darussalam for regulatory and safety monitoring.

The data gap in food safety regulations have created misinformation leading to the rejection of commodities for trade. The evidence presented is the local regulation of arsenic in sea produce which is based on total arsenic, tAs, instead of toxic inorganic arsenic, iAs. Furthermore, tAs data in animal origin seafood has been widely proven to be dominated by the non-toxic Arsenobetaine, AsB. Therefore, if arsenic regulatory limit was set based only on tAs without reference to iAs data, seafood products might be wrongfully rejected for trade because of non-compliance to tAs limit. We provided analysis of tAs and iAs of 14 local prawn and shrimp commodities from three shrimp/prawn sector namely aquaculture (n = 3), capture (n = 5) and processed (n = 6) using effective extraction, as well as, a fit-for-purpose analytical method for iAs. A HVG-AAS method was developed and validated for iAs with LoQ of 1.6 ppb, analytical range of 0-6 ppb, repeatability RSDr of 0.5-3.1 %, coefficient of determination R2 of 0.9975, and percentage recovery of 90.9 %, while an existing method using ICP-MS was used to verify the tAs. Based on the AOAC Official Method 999.10 2005 with minor adjustments, seafood samples were digested with concentrated nitric acid and hydrogen peroxide under pressure in a closed vessel heated by a microwave digester. An additional step for iAs determination was necessary to ensure compatibility in HVG-AAS analysis. Further subdivision of the aquaculture and capture samples was done by dividing them into 3 fractions, namely head, flesh and peel. Comparison of tAs in all the three fractions indicated that for aquaculture sector, the highest tAs were found in the flesh (2nd highest in % weight) whereas for the capture sector, the highest amount of tAs correlated with the highest % weight of the fraction. On regulatory aspects, speciation analysis on the iAs indicated samples with quantifiable iAs value were in-compliance despite tAs were initially found to be higher than the national limits. Risk assessment of iAs indicated there were no risk for human daily intake based on the BDML0.5 value of 3.0 µg/kg b.w per day for an average 70 kg man. All findings concluded the need for doing arsenic speciation analysis of iAs along with tAs for routine monitoring of prawn/shrimp samples and to revise the local limits from tAs to iAs particularly for seafood commodities.

Seasonal variation of arsenic in PM10 and PMx in an urban park: The influence of vegetation-related biomethylation on the distribution of its organic species and air quality.

Arsenic (As) levels in particulate matter (PM) are routinely monitored in cities of developed countries. Despite advances in the knowledge of its inorganic species in PM in urban areas, organic species are often overlooked with no information on their behaviour in urban parks - areas with increased potential for As biomethylation. Therefore, the aim of this study was to characterize As distribution, bioaccessibility, seasonal variation and speciation (AsIII, AsV, MMA, DMA and TMAO) in PMx-PM10 of an urban park. Two sites with different distance from the road were selected for winter and summer sampling. From the PM samples, we gravimetrically determined PM10 concentrations in the air and via ICP-MS the total As content there. To assess the portion of bioaccessible As, water extractable As content was analysed. Simultaneously, the As species in PM10 water extracts were analysed via coupling of HPLC with ICP-MS method. There was no seasonal difference in PM10 concentration in the park, probably due to the increased summer PM load related to recreational activities in the park and park design. Spatial distribution of total As in PM10 and As fractional distribution in PMx suggested that As mostly didn't originate from traffic although highest As content was observed in the fine fraction (PM2.5) related to combustion processes. However, significant winter increase of As (determined by AsIII and AsV) despite the unchanged concentration of PM10 indicated a decisive influence of household heating-related combustion and possibly influence of reduced vegetation density. As present in the PM10 was mostly in bioaccessible form. Seasonal influence of As biomethylation was clearly demonstrated on the TMAO specie during the summer campaign. Except the significant summer TMAO increase, the results also indicated the biomethylation influence on DMA. Therefore, an increased risk of exposure to organic As species in urban parks can be expected during summer.

Optimizing Antimony Speciation Analysis via Frontal Chromatography-ICP-MS to Explore the Release of PET Additives.

Antimony (Sb) contamination poses significant environmental and health concerns due to its toxic nature and widespread presence, largely from anthropogenic activities. This study addresses the urgent need for an accurate speciation analysis of Sb, particularly in water sources, emphasizing its migration from polyethylene terephthalate (PET) plastic materials. Current methodologies primarily focus on total Sb content, leaving a critical knowledge gap for its speciation. Here, we present a novel analytical approach utilizing frontal chromatography coupled with inductively coupled plasma mass spectrometry (FC-ICP-MS) for the rapid speciation analysis of Sb(III) and Sb(V) in water. Systematic optimization of the FC-ICP-MS method was achieved through multivariate data analysis, resulting in a remarkably short analysis time of 150 s with a limit of detection below 1 ng kg-1. The optimized method was then applied to characterize PET leaching, revealing a marked effect of the plastic aging and manufacturing process not only on the total amount of Sb released but also on the nature of leached Sb species. This evidence demonstrates the effectiveness of the FC-ICP-MS approach in addressing such an environmental concern, benchmarking a new standard for Sb speciation analysis in consideration of its simplicity, cost effectiveness, greenness, and broad applicability in environmental and health monitoring.

Update on chromium speciation analysis in foods: a review of advances in analytical methods and dietary exposure assessment.

Chromium occurs naturally in different oxidation states. Amongst them, hexavalent chromium is classified as both genotoxic and carcinogenic while trivalent chromium can be considered as an essential element. Therefore, speciation analysis is essential when conducting dietary exposure assessment. Several critical reviews have been published on chromium speciation analysis in foodstuffs in the last decade. However, a method that can account for species interconversion during the extraction procedure has not been reported in the reviews. In recent years, an online method using species-specific isotope dilution mass spectrometry has been developed for the simultaneous determination of trivalent and hexavalent chromium in foodstuffs. Apart from that, new methods based on offline analytical techniques, to analyse trivalent and hexavalent chromium separately, are still under development. Therefore, one of the objectives of this paper is to review these recently published analytical methods and assess whether they are fit for chromium speciation analysis in foodstuffs. Additionally, an objective is also to assess whether their limits of detection are sufficiently low for dietary exposure assessment with respect to the neoplastic effects of hexavalent chromium. Moreover, possible future research gaps are identified based on the current knowledge and existing literature.

One-pot preparation of magnetic composite containing boronic acid groups and aminated multwalled carbon nanotubes for the speciation of Se(IV) and Se(VI) in water and milk samples by combination with chromatographic quantification.

Speciation of Se(IV) and Se(VI) is essential due to their significant differences in reactivity, toxicity and bioavailability. Efficient extraction is the pivotal step in the quantification of inorganic selenium species. In this work, a new magnetic nano-composite (MNC) containing boronic acid group and aminated multwalled carbon nanotubes was facilely fabricated by means of one-pot hydrothermal strategy. The prepared MNC contained abundant functional groups and satisfactory magnetic saturation value. Combining with magnetic solid phase extraction (MSPE) format, the MNC displayed satisfactory capture performance towards the complex formed by the coordination of Se(IV) and o-phenylenediamine (OPA). Adsorption isotherm and adsorption kinetics were studied in detail to investigate the adsorption procedure of Se(IV)/OPA complex on MNC. Under the optimal preparation conditions of MNC and extraction parameters, the MNC/MSPE was connected with HPLC equipped with a diode array detector (DAD) to quantify trace Se(IV) and Se(VI) species in water and milk samples. Se(VI) was reduced to Se(IV) and then the total inorganic Se was quantified by the developed method. Subtraction method was used to measure the concentration of Se(VI). The achieved limits of detection were in the ranges of 0.0082-0.013 µg/L and 0.041-0.13 µg/kg for water and milk samples, respectively. Recoveries in actual samples spiked with different amounts of analytes varied from 81.0 % and 117 %, and the RSDs for repeatability varied from 1.0 % to 10 %. In comparison with existing studies based on MSPE, the established method presents some merits such as greenness in the preparation of magnetic adsorbent, rapid extraction procedure, low cost and satisfactory sensitivity in the speciation of inorganic Se species.

Selenium nanoparticles in aquaculture: Unique advantages in the production of Se-enriched grass carp (Ctenopharyngodon idella).

The production of selenium-enriched fish can contribute to alleviating selenium deficiency in human diets. However, it is still unclear which selenium source, as an additive, can efficiently and cost-effectively produce high-quality selenium-enriched fish. This study evaluated the effects of selenium nanoparticles (SeNP), selenite, and selenomethionine (SeMet) on the growth, antioxidant capacity, selenium content, selenium speciation, and meat quality of grass carp. Ten diets were prepared, including a basal diet (BD) and three concentrations (0.1, 0.3, and 0.9 mg/kg) of SeNP, selenite, and SeMet. A total of 600 fish (250.79 ± 1.57 g) were randomly assigned to 30 tanks (3 tanks/group). Fish were fed the experimental diet three times daily for 60 d. In this study, SeNP most significantly promoted the growth and antioxidant capacity of grass carp, with 0.3 mg/kg SeNP identified as the optimal additive concentration. Additionally, SeNP demonstrated equally excellent bioavailability as SeMet and significantly increased the content of SeMet in grass carp (Ctenopharyngodon idella) muscle. Furthermore, compared to SeMet and selenite, dietary SeNP could more significantly enhance the content of selenocysteine (SeCys2) and methylselenocysteine (MeSeCys) in grass carp muscle tissue. In addition, we have demonstrated that SeCys2 and MeSeCys promote apoptosis of cancer cells (HeLa) through the mitochondrial apoptotic pathway (involving Bax and Bcl-2). Furthermore, as an additive, 0.3 mg/kg SeNP significantly improved the flesh quality of grass carp by reducing crude fat and heavy metal content, as well as increasing the levels of eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) and the ratio of n-3/n-6 polyunsaturated fatty acid (PUFA). In summary, SeNP is the most suitable additive for producing selenium-enriched fish.

A screening for optimal selenium enrichment additives for selenium-enriched fish production: Application of a HPLC-ICP-MS method.

The production of selenium-enriched fish contributes to alleviating selenium deficiency for humans. In this study, selenium nanoparticles (SeNPs) comparable in bioavailability to selenomethionine (SeMet), increased SeMet content in O. macrolepis (Onychostoma macrolepis) muscle. Additionally, dietary SeNPs significantly enhanced selenocysteine (SeCys2) and methylselenocysteine (MeSeCys) levels in O. macrolepis muscle. The effect of SeNPs on selenium speciation in grass carp muscle was consistent with O. macrolepis results. SeCys2 and MeSeCys showed antioxidant capacity in HEK293T cells, indicating enhanced health benefits of Se-enriched fish produced using SeNPs. Furthermore, the addition of 0.3 mg/kg SeNPs significantly improved the flesh quality of O. macrolepis by reducing the content of crude fat and heavy metals, as well as increasing the levels of crude protein, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), and the ratio of n-3/n-6 polyunsaturated fatty acids (PUFAs). Therefore, selenium-enriched fish produced from SeNPs is a good source for improving human dietary selenium intake.

Rapid determination of chromium species in environmental waters using a diol-bonded polymer-stationary column under water-rich conditions coupled with ICPMS.

Chromium speciation analysis in environmental water is of great significance for the monitoring of water pollution and assessing its influences on human health. This study proposes a rapid analytical approach for the simultaneous determination of Cr(VI) and Cr(III) in environmental waters by hydrophilic interaction chromatography (HILIC) coupled with ICPMS under a water-rich condition. 2,6-Pyridinedicarboxylic acid (PDCA) was used to unify Cr(III) species in various chemical forms into a stable Cr(III)-PDCA anion complex and then separated from Cr(VI) oxyanion on a diol-bonded polymer-based HILIC column. An aqueous mobile phase containing 50 mmol L-1 ammonium acetate (pH 7.0), 2 mmol L-1 PDCA, and 4% acetonitrile successfully separates chromium species as well as chloride ions. In addition, our method elutes Cr(VI) preferentially over Cr(III)-PDCA, enabling rapid determination of Cr(VI), and both chromium species were analyzed within 6.2 min. The detection limits of 0.19 µg L-1 for Cr(VI) and 0.35 µg L-1 for Cr(III) at m/z 52 under He collision mode are comparable to or better than the conventional ion exchange chromatography-ICPMS methods, and quantitative recovery was obtained from spike-recovery tests on river water samples containing various levels of matrix. Optimization experiments of the HPLC conditions indicate that the retentions of Cr(VI) and Cr(III)-PDCA are characterized by electrostatic and nonpolar interactions, respectively. The retention behavior of inorganic anions and cations in water-rich conditions observed in this study will provide new insights into the separation mechanism in polymer-based HILIC columns, which has been poorly understood.

Task specific microextraction column based on monolith for magnetic field-assisted in-tube solid phase microextraction of vanadium species in complex samples prior to online chromatographic analysis.

The dominant species of vanadium (V) are V(IV) and V(V) which exhibit different toxicity and biological effects. Thus, speciation of V(IV) and V(V) is highly essential. Efficient sample preparation is the core step in the quantification of V(IV) and V(V). In the present study, a new task specific microextraction column based on monolith mingled with Fe3O4 nanoparticles (MBMC) was in situ synthesized in capillary and utilized as the extraction phase of magnetic field-assisted in-tube solid phase microextraction (MA-IT-SPME) of V(IV) and V(V) species which were coordinated with ethylene diamine tetraacetic acid (EDTA). The prepared MBMC presented porous and superparamagnetic properties, and possessed abundant functional groups. Results revealed that the exertion of magnetic field during adsorption and eluting steps boosted the extraction efficiency of V(IV)-EDTA and V(V)-EDTA chelates from 65.1 % to 55.7 %-90.0 % and 80.1 %, respectively. Under the beneficial extraction parameters, the established MA-IT-SPME was online hyphenated with HPLC/DAD to perform speciation of trace vanadium in water and vegetable samples, the achieved limits of detection were 0.054-0.060 µg/L and 1.4-1.5 µg/kg in water and vegetable samples, respectively, and the spiked recoveries varied from 82.5 to 118 %. In addition, relevant extraction mechanism under magnetic field was explored. In comparison with existing methods, the developed MA-IT-SPME technique displays some attractive merits such as automation, good anti-interference ability, high extraction efficiency, low cost and less use of organic solvent, in the capture of V species. The established online MBMC@MA-IT-SPME-HPLC/DAD system can become a competitive approach for sensitive speciation of V(IV) and V(V) at trace levels in complex samples.

Speciation analysis and toxicity evaluation of arsenolipids-an overview focusing on sea food.

Arsenic, which can be divided into inorganic and organic arsenic, is a toxic metalloid that has been identified as a human carcinogen. A common source of arsenic exposure in seafood is arsenolipid, which is a complex structure of lipid-soluble organic arsenic compounds. At present, the known arsenolipid species mainly include arsenic-containing fatty acids (AsFAs), arsenic-containing hydrocarbons (AsHCs), arsenic glycophospholipids (AsPLs), and cationic trimethyl fatty alcohols (TMAsFOHs). Furthermore, the toxicity between different species is unique. However, the mechanism underlying arsenolipid toxicity and anabolism remain unclear, as arsenolipids exhibit a complex structure, are present at low quantities, and are difficult to extract and detect. Therefore, the objective of this overview is to summarize the latest research progress on methods to evaluate the toxicity and analyze the main speciation of arsenolipids in seafood. In addition, novel insights are provided to further elucidate the speciation, toxicity, and anabolism of arsenolipids and assess the risks on human health.