Characterization of arsenic species by liquid sampling-atmospheric pressure glow discharge ionization mass spectrometry.

A liquid sampling-atmospheric pressure glow discharge (LS-APGD) ionization source operating at a nominal power of 30 W and solution flow rate of 30 µL min-1 and supported in a He sheath gas flow rate of 500 mL min-1 was interfaced to an Orbitrap mass spectrometer and assessed for use in rapid identification of inorganic and organic arsenic species, including As(III), As(V), monomethylarsonic acid, dimethylarsinic acid, and arsenobetaine in a 2% (v/v) nitric acid medium. Mass spectral acquisition in low-resolution mode, using only the ion trap analyzer, provided detection of protonated molecular ions for AsBet (m/z 179), DMA (m/z 139), MMA (m/z 141), and As(V) (m/z 143). As(III) is oxidized to As(V), likely due to in-source processes. Typical fragmentation of these compounds resulted in the loss of either water or methyl groups, as appropriate, i.e., introducing DMA also generated ions corresponding to MMA and As(V) as dissociation products. Structure assignments were also confirmed by high-resolution Orbitrap measurements. Spectral fingerprint assignments were based on the introduction of solutions containing 5 µg mL-1 of each arsenic compound.

Production and certification of BOTS-1: bovine muscle-certified reference material for incurred veterinary drug residues.

A freeze-dried bovine muscle-certified reference material (CRM), known as BOTS-1 (DOI: https://doi.org/10.4224/crm.2018.bots-1 ), containing incurred residues of commonly used veterinary drugs was produced and certified for the mass fraction of eight veterinary drug residues. Value assignment was carried out using liquid chromatography tandem mass spectrometry (LC-MS/MS) methods in conjunction with isotope dilution and standard addition approaches involving stable isotope internal standards. Data from the National Research Council of Canada (NRC), Canadian Food Inspection Agency (CFIA), United States Department of Agriculture (USDA), and the Federal Office of Consumer Protection and Food Safety in Germany (BVL) were used for value assignment. Results for two drug residues were also obtained through an international inter-laboratory comparison CCQM-K141/P178 organized under the auspices of the International Bureau of Weights and Measures (BIPM). Quantitative NMR (1H-qNMR) was used to characterize primary standards of all veterinary drugs certified. The certified mass fractions of the veterinary drug residues were 490 ± 100 µg/kg for chlorpromazine, 44 ± 4.4 µg/kg for ciprofloxacin, 3.3 ± 1.4 µg/kg for clenbuterol, 9.5 ± 0.8 µg/kg for dexamethasone, 57 ± 4.8 µg/kg for enrofloxacin, 3.0 ± 0.4 µg/kg for meloxicam, 12.4 ± 1.2 µg/kg for ractopamine, and 2290 ± 120 µg/kg for sulfadiazine with expanded uncertainties quoted (95% confidence) which include the effects due to between-bottle inhomogeneity, instability during long-term storage and transportation, and characterization.

Comparison of Carbon Isotope Ratio Measurement of the Vanillin Methoxy Group by GC-IRMS and 13C-qNMR.

Site-specific carbon isotope ratio measurements by quantitative 13C NMR (13C-qNMR), Orbitrap-MS, and GC-IRMS offer a new dimension to conventional bulk carbon isotope ratio measurements used in food provenance, forensics, and a number of other applications. While the site-specific measurements of carbon isotope ratios in vanillin by 13C-qNMR or Orbitrap-MS are powerful new tools in food analysis, there are a limited number of studies regarding the validity of these measurement results. Here we present carbon site-specific measurements of vanillin by GC-IRMS and 13C-qNMR for methoxy carbon. Carbon isotope delta (δ13C) values obtained by these different measurement approaches demonstrate remarkable agreement; in five vanillin samples whose bulk δ13C values ranged from -31‰ to -26‰, their δ13C values of the methoxy carbon ranged from -62.4‰ to -30.6‰, yet the difference between the results of the two analytical approaches was within ±0.6‰. While the GC-IRMS approach afforded up to 9-fold lower uncertainties and required 100-fold less sample compared to the 13C-qNMR, the 13C-qNMR is able to assign δ13C values to all carbon atoms in the molecule, not just the cleavable methoxy group.

Determination of selenium-containing species, including nanoparticles, in selenium-enriched Lingzhi mushrooms.

Mushrooms are considered a valuable food source due to their high protein and fibre and low fat content, among the other health benefits of their consumption. Selenium is an essential nutrient and is renowned for its chemo-preventative properties. In this study, batches of selenium-enriched Lingzhi mushrooms were prepared by growing mycelium and fruit in substrates containing various concentrations of sodium selenite. The mushroom fruit accumulated low levels of selenium with selenomethionine being the most abundant form in all enriched samples. Conversely, the mycelium showed significant selenium accumulation but relatively low proportions of selenomethionine. The red colour of the selenium-enriched mycelia indicated the probable presence of selenium nanoparticles, which was confirmed by single-particle inductively coupled plasma-mass spectrometry. Mean particle diameters of 90-120 nm were observed, with size distributions of 60-250 nm. Additional analysis with transmission electron microscopy confirmed this size distribution and showed that the biogenic selenium nanoparticles were roughly spherical in shape and contained elemental selenium.

Methylation and bio-accessibility assessment of arsenate in crickets (Gryllusbimaculatus).

The ability of an organism to biomethylate toxic inorganic arsenic (As) determines both, the amount of As available for uptake higher up the food chain and the toxicity of bioavailable As. An exposure study was conducted to determine ability of farmed crickets to metabolize dietary arsenate. Crickets were exposed to 1.3 ± 0.1, 5.1 ± 2.5 and 36.3 ± 5.6 mg kg-1 dietary arsenate and quantitation of total As showed retention of 0.416 ± 0.003, 1.3 ± 0.04 and 2.46 ± 0.09 mg kg-1, respectively. Speciation analysis revealed that crickets have well developed ability to biomethylate dietary arsenate and the most abundant methylated As compound was DMA followed by MMA, TMAO and an unknown compound. Arsenobetaine, although present in all feed, control and As-rich, was measured only in the control crickets. To assess the bio-accessibility of the As species, crickets were subjected to simulated gastrointestinal digestion. The results showed that majority of As was extracted in saliva, followed by gastric and intestinal juice, which mass fraction was equal to residue. Over 78% of total As was shown to be bio-accessible with methylated species reaching 100% and iAs over 79% bio-accessibility. Additionally, arsenite and arsenate have shown different distributions between sequential leachate solutions. Bioaccumulation of As was observed in the studied crickets although it does not seem to occur to the same extent at higher exposure levels.

82Se Metabolically-Labeled Yeast as a Matrix-Matched Isotope Dilution Standard for Quantification of Selenomethionine.

Selenized yeast is commonly used as a highly bioavailable source of selenium in dietary supplements and feed additives and is used in research settings in various disciplines due to the large number of selenium-containing metabolites formed during growth. With the selenomethionine being the major form of selenium present in selenized yeasts, its accurate quantitation is essential, however, values are frequently underestimated due to the costly and time-consuming hydrolysis-based sample preparation required to release the selenoamino acid from proteins for analysis. The National Research Council Canada has developed an 82-Se-enriched selenized yeast Certified Reference Material, SEEY-1 (DOI: 10.4224/crm.2023.seey-1) intended to be used as a matrix-matched spike material for isotope dilution analysis of selenized yeasts. The total selenium and selenomethionine contents of SEEY-1 were determined to be 322.1 ± 4.8 mg/kg (k = 2) and 635.6 ± 16.8 mg/kg (k = 2), respectively. Here we present results on the preparation of the 82-Se-enriched yeast, the certification process, and provide an example of the use of SEEY-1 as a matrix-matched spike for the analysis of selenomethionine in a sample of selenized yeast. We demonstrate here that SEEY-1 is able to compensate for the partial digestion of yeast proteins and provide reliable analytical data on Se amino acid content in under an hour instead of the 16 hours required for conventional complete acid hydrolysis.

Characterization of vanillin carbon isotope delta reference materials.

Stable carbon isotope ratio measurements are used to investigate the provenance of vanillin. In this study, a variety of commercial vanillin samples and vanilla products were analyzed to provide a frame of reference for the variability of carbon isotope delta values in various vanillin samples, with the results ranging from -20.6 to -36.7‰ relative to the Vienna Peedee Belemnite (VPDB). We present information on the development of two synthetic vanillin reference materials, VANA-1 and VANB-1, prepared in 0.75 g units in glass vials, to be used for the calibration of carbon isotope delta measurements of vanillin and other easily combustible organic materials. Characterization of 40 vials each of VANA-1 and VANB-1 was performed by three laboratories over several measurement sequences. The certified carbon isotope delta values are -31.30 ± 0.06‰ (VANA-1) and -25.85 ± 0.05‰ (VANB-1). These uncertainties, for the 95% confidence level, include considerations for measurement uncertainty, coherence of the reference materials used for calibration, batch homogeneity, and stability during storage and transportation. The results are traceable to the VPDB through a set of nine reference materials (IAEA-CH-6, USGS65, IAEA-600, NBS22, USGS61, IAEA-603, IAEA-610, IAEA-611, and IAEA-612). For up to date certified values, users should refer to doi.org/10.4224/crm.2022.vana-1 and doi.org/10.4224/crm.2022.vanb-1.

Site-specific carbon isotope measurements of vanillin reference materials by nuclear magnetic resonance spectrometry.

Vanillin, one of the world's most popular flavor used in food and pharmaceutical industries, is extracted from vanilla beans or obtained (bio)-synthetically. The price of natural vanillin is considerably higher than that of its synthetic alternative which leads increasingly to counterfeit vanillin. Here, we describe the workflow of combining carbon isotope ratio combustion mass spectrometry with quantitative carbon nuclear magnetic resonance spectrometry (13C-qNMR) to obtain carbon isotope measurements traceable to the Vienna Peedee Belemnite (VPDB) with 0.7‰ combined standard uncertainty (or expanded uncertainty of 1.4‰ at 95% confidence level). We perform these measurements on qualified Bruker 400 MHz instruments to certify site-specific carbon isotope delta values in two vanillin materials, VANA-1 and VANB-1, believed to be the first intramolecular isotopic certified reference material (CRMs).

From sea salt to seawater: a novel approach for the production of water CRMs.

Natural water certified reference materials (CRMs) are mostly available in a liquid form, and they are produced starting from suitable environmental samples. Many precautions are usually needed to avoid biological or physical degradation, including filtration, acidification, and sterilization. In this study, the drawbacks associated with liquid-based seawater CRMs were tackled by developing a salt-based seawater proxy for nutrients that could be reconstituted in water solution just before use. Phosphate, silicate, and nitrate were chosen as target analytes. Sea salt mimicking the composition of seawater was spiked with an aqueous solution of the analytes and homogenized using a high-energy planetary ball mill (uhom < 1.2%). The salt powder CRM SALT-1 ( https://doi.org/10.4224/crm.2022.salt-1 ) demonstrated good short- and long-term stability for nutrients. When the SALT-1 was reconstituted in water at the 4.0% w/w level, the resulting solution had similar properties with respect to typical seawater in terms of major constituents (± 20%), trace metals, density (1.023 g/mL), pH (8.8-9.0), and optical properties relevant to the photometric characterization. Phosphate and silicate were quantified by photometry (molybdenum blue method, batch mode), whereas nitrate was quantified by isotope dilution GC-MS (uchar < 1.2%). In the SALT-1 reconstituted seawater solution at the 4.0% w/w salt level, the nutrient amount concentration was w(phosphate, PO43-) = 1.615 ± 0.030 µmol/L, w(silicate as SiO2) = 8.89 ± 0.31 µmol/L, and w(nitrate, NO3-) = 18.98 ± 0.45 µmol/L at the 95% confidence (k = 2). Overall, the SALT-1 CRM exhibits similar nutrient profile and general analytical characteristics as the MOOS-3 CRM. However, the SALT-1 has much reduced preparation, storage, and distribution cost, likely much better long-term stability, and it could enable the production of lower cost and more accessible seawater reference materials.

Determination of Metallic Impurities in Carbon Nanotubes by Glow Discharge Mass Spectrometry.

A method for the rapid assessment of metallic impurities in carbon nanotubes (CNTs) by pin-cell source geometry glow discharge mass spectrometry (GDMS) is presented. Pins were prepared by pressing CNT powder onto an indium substrate. GDMS analysis was performed using high-carbon-content nanotube and coal-certified reference materials for calibration purposes. This approach enables the calibrated measurement of 41 elemental impurities in CNTs. The method was validated by the analysis of NIST SRM 2483 single-wall CNTs (raw soot) with good agreement with the certified values. The proposed measurement approach could also be applied not only for CNTs but also for the assessment of precursor materials used in the synthesis of CNTs and for quality control during the entire manufacturing process. The ability to assess the presence of all metallic impurities in a simple, reliable, high-throughput manner will allow the industry to real-time monitor any changes in the product process, access its toxicity, and environmental impact. As sample preparation is maintained to a minimum, this allows the determination of metallic impurities at concentration levels that are usually not attainable by most techniques.

Collaborative determination of trace element mass fractions and isotope ratios in AQUA-1 drinking water certified reference material.

The Isotrace CNRS workgroup in collaboration with National Research Council of Canada has characterized a number of trace element mass fractions and isotope ratios currently not certified in AQUA-1 natural drinking water reference material (NRC Canada). This survey further expands the use of this material as a tool for environmental quality control, method validation, and method development tool for the international community. Simultaneously, the SLRS-6 river water was analyzed as quality control and also in order to compare both water characteristics, which were sampled in the same area but having undergone different treatment. Mass fractions for B, Cs, Li, Ga, Ge, Hf, Nb, P, Rb, Rh, Re, S, Sc, Se, Si, Sn, Th, Ti, Tl, W, Y, Zr, REEs, and six isotopic ratios are proposed for Sr and Pb. Measurements were mostly performed using ICP-MS with various calibration approaches. The results are reported as consensus or indicative values depending on the number of available datasets, with their associated uncertainties.

Discontinuity in the Realization of the Vienna Peedee Belemnite Carbon Isotope Ratio Scale.

By convention, carbon isotope ratios are expressed relative to VPDB defined by the calcite standard NBS19 in the 1980s. [See T. Coplen, Pure Appl. Chem. 1994, 66, 273-276.] To improve the realization of the VPDB scale, a second fixed point (lithium carbonate, LSVEC) was introduced in 2006 [T. Coplen et al. Anal. Chem. 2006, 78, 2439-2441], which is now known to be isotopically unstable. [Assonov, S. Rapid Commun. Mass Spectrom., 2018, 32, 827-830.] With the high-quality reference materials made available in 2020, it is now possible to realize the VPDB scale with high confidence. [Assonov, S. et al. Rapid Commun. Mass Spectrom., 2020, 34, e8867; Assonov, S. Rapid Commun. Mass Spectrom. 2021, 35, e9014; Qi, H. et al. Rapid Commun. Mass Spectrosc. 2021, 35, e9006.] Here, we report the analysis of 25 reference materials using isotope ratio combustion mass spectrometry, show the discontinuity between the values measured against the new IAEA reference materials and the values currently assigned to these reference materials on the VPDB2006, and provide a link bringing these materials onto the new VPDB2020.

Compilation of selenium metabolite data in selenized yeasts.

Selenium-enriched yeast has long been recognized as an important nutritional source of selenium and studies have suggested that supplementation with this material provides chemo-preventative benefits beyond those observed for selenomethionine supplementation, despite the fact that selenomethionine accounts for 60-84% of the total selenium in selenized yeasts. There is much ongoing research into the characterization of the species comprising the remaining 16-40% of the selenium, with nearly 100 unique selenium-containing metabolites identified in aqueous extracts of selenized yeasts (Saccharomyces cerevisiae). Herein, we discuss the analytical approaches involved in the identification and quantification of these metabolites, and present a recently created online database (DOI: 10.4224/40001921) of reported selenium species along with chemical structures and unique mass spectral features.

Ash-Decorated and Ash-Painted Soot from Residual and Distillate-Fuel Combustion in Four Marine Engines and One Aviation Engine.

Soot is typically the dominant component of the nonvolatile particles emitted from internal combustion engines. Although soot is primarily composed of carbon, its chemistry, toxicity, and oxidation rates may be strongly influenced by internally mixed inorganic metal compounds (ash). Here, we describe the detailed microstructure of ash internally mixed with soot from four marine engines and one aviation engine. The engines were operated on different fuels and lubrication oils; the fuels included four residual fuels and five distillate fuels such as diesel, natural gas, and Jet A-1. Using annular-dark-field scanning transmission electron microscopy (ADF-STEM), we observed that ash may occur either as distinct nodules on the soot particle (decorated) or as continuous streaks (painted). Both structures may exist within a single particle. Decorated soot was observed for both distillate and residual fuels and contained elements associated with either the fuel (V, Ni, Fe, S) or with the lubrication oil (Zn, Ca, P). Painted soot was observed only for residual-fuel soot, and only contained elements associated with the fuel. Additional composition measurements by inductively coupled plasma mass spectrometry (ICP-MS) of filter samples indicated that the internal mixing trends of ash with soot were consistent with the overall ash-to-carbon ratio of the sampled combustion aerosols. Painted soot may form when molten ash coagulates with or condenses onto soot within engines.

A mass spectrometric study of hydride generated arsenic species identified by direct analysis in real time (DART) following cryotrapping.

Hydride generation (HG) coupled to cryotrapping was employed to introduce, separately and with high selectivity, four gaseous arsanes into a direct analysis in real time source for high-resolution mass spectrometry (DART-HR-MS). The arsanes, i.e., arsane (AsH3), methylarsane (CH3AsH2), dimethylarsane ((CH3)2AsH), and trimethylarsane ((CH3)3As), were formed under HG conditions that were close to those typically used for analytical purposes. Arsenic containing ion species formed during ambient ionization in the DART were examined both in the positive and negative ion modes. It was clearly demonstrated that numerous arsenic ion species originated in the DART source that did not accurately reflect their origin. Pronounced oxidation, hydride abstraction, methyl group(s) loss, and formation of oligomer ions complicate the identification of the original species in both modes of detection, leading to potential misinterpretation. Suitability of the use of the DART source for identification of arsenic species in multiphase reaction systems comprising HG is discussed.

Tessier sequential extraction on 17 elements from three marine sediment certified reference materials (HISS-1, MESS-4, and PACS-3).

The four-step Tessier sequential extraction procedure is a well-known approach used for environmental and geochemical studies in soil and sediments. However, a lack of reference materials limits its use making implementation and quality control cumbersome. This study applied Tessier sequential extraction to three globally used marine sediment certified reference materials (CRMs) including HISS-1, MESS-4, and PACS-3 with varying levels of contamination. The study analyzed the distribution of 17 elements throughout the extraction phases. Overall, the percent recovery (sum of steps vs total metal concentration) of all analyzed elements in Tessier extraction was 92% + 40% in HISS-1, 101% + 12% in MESS-4, and 102% + 10% in PACS-3. The observed uncertainty of the individual elemental concentrations averaged at 13%, which compares favorably with the 16% target uncertainty derived from the Horwitz equation. The reference data set produced here using the Tessier sequential extraction procedure will serve as a quality control and method development tool for laboratories. Graphical abstract.

Determination of 27 metals in HISS-1, MESS-4 and PACS-3 marine sediment certified reference materials by the BCR sequential extraction.

The BCR sequential extraction procedure developed by the European Community Bureau of Reference was applied to the three marine sediment certified reference materials (CRMs). These CRMs are designated as HISS-1, MESS-4, and PACS-3 and comprise respectively pristine, moderately-contaminated, and highly-contaminated sediments, respectively. The study aimed to provide values of extractable elements in reference materials of varied geological origin to support method development and quality control efforts. Concentrations of 27 elements extracted in the three sequential extraction steps and in the residue were determined. The extraction steps consisted of: Step 1 - acetic acid extraction (targeting the exchangeable, water- and acid-soluble fraction); Step 2 - hydroxylammonium chloride extraction (targeting the reducible fraction); and Step 3 - hydrogen peroxide extraction (targeting the oxidizable fraction). The results from two independent laboratories using the sequential extraction procedure for the 27 elements were combined using the DerSimonian-Laird method of analysis implemented in the NIST Consensus Builder software. The percent recovery (sum steps vs total metal content) of 27 elements ranged from 68% to 125% in HISS-1, 76%-119% in MESS-4, and 70%-125% in PACS-3, based on the certified values. The combined uncertainty (k = 2) was from 1% to 39% for HISS-1, 3%-45% for MESS-4, and 3%-21% for PACS-3. Comparing the three extraction steps, the uncertainty of Step 3 was the highest for all the three CRMs. The agglomerate sediments in MESS-4 resulted in high uncertainty when compared to HISS-1 and PACS-3. The method validation showed the BCR sequential extraction procedure can apply to other elements including As, Co, Li, Mn, and V.

Novel Approach for the Accurate Determination of Se Isotope Ratio by Multicollector ICP-MS.

In this work, a method for the accurate and precise determination of 82Se/78Se isotope ratio in natural samples of environmental and biological origin, using multicollector inductively coupled plasma mass spectrometry in a wet plasma mode without using neither hydride generation nor separation of Se, was developed. It was based on the optimized regression model with standard-sample bracketing (ORM-SSB) to efficiently correct instrumental isotopic fractionation/mass bias and matrix effects. In addition, three mass bias correction models of SSB alone, SSB combined with internal standard (IS-SSB), and ORM-SSB were compared for the Se isotope ratio measurements. NIST SRM 987 Sr was used as an internal standard, and the reproducibility of the results obtained with the proposed method was verified by measuring NIST SRM 3149 standard over different days (nine independent measurement sessions). Delta values of the 82Se/78Se isotope ratio were measured in selenium-enriched yeast-certified reference material SELM-1, natural selenomethionine samples, and model solutions of artificial seawater. Solutions obtained after thiol resin treatment were measured to demonstrate the applicability of the proposed method in eliminating matrix effects due to residual of thiol resin in the sample solutions. Among three mass bias correction models, ORM-SSB correction model proved to be the best to eliminate the matrix effects and instrumental drift. IS-SSB model offered also a good precision but was slightly less accurate. Both models showed good robustness against effects of different sample matrices. Finally, the SSB alone could not be recommended for Se isotope analysis as it produces inaccurate and imprecise results.

Application of direct analysis in real time to study chemical vapor generation mechanisms: reduction of dimethylarsinic(V) acid with aqueous NaBH4 under non-analytical conditions.

The aqueous-phase reaction of dimethylarsinc acid (DMAs(V)) with NaBH4 (THB) was studied under non-analytical conditions (1000 µg/mL As, 0.1 M HCl, 1% NaBH4) with the aim of identifying intermediates and reaction products. The use of direct analysis in real time (DART) with high-resolution mass spectrometry (HRMS), in combination with two different chemical vapor generation systems, allowed the identification of some species not detected by GC-MS such as Me2As-AsMe-AsMe2 and the arsonium species [Me3As-AsMe2]+ and [Me2As-AsMe2-AsMe2]+. Many other methylated species of arsenic containing up to four arsenic atoms have been observed. Unfortunately, the oxidation mechanism that took place in the DART source interfered with the identification of some of those species formed in solution following THB reduction. The species identified by DART-HRMS, together with those previously identified by GC-MS (Me2AsH, Me2AsOH, Me3As, Me3AsO, Me2AsAsMeH, Me2AsAsMe2, and Me2As-O-AsMe2)' enabled the formulation of hypotheses on the possible reaction pathways and revealed an aqueous-phase reactivity of DMAs(V) which could not be explained on the basis of current knowledge. Graphical Abstract.

Arsenic speciation in sea cucumbers: Identification and quantitation of water-extractable species.

With the constant quest for new sources of superfoods to supplement the largely nutrient deficient diet of the modern society, sea cucumbers are gaining increasing popularity. Three species of sea cucumbers, Cucumaria frondosa, Apostichopus californicus and Apostichopusjaponicus were collected from three geographical regions, Atlantic and Pacific coast of Canada and Yellow sea/ East China sea in China, respectively. These organisms were sectioned into parts (body wall, tentacles, internal organ, skin and muscle) and analysed for total arsenic (As) by inductively coupled plasma mass spectrometry (ICP-MS) and As species by high-performance liquid chromatography (HPLC) coupled to ICP-MS. Normal and reversed sequential extractions were optimised to address As distribution between lipids (polar and non-polar) and water-extractable fractions. Two extraction methods for water-extractable As were compared in terms of the number and the amount of extracted species. The results revealed that total As concentration and As species distribution varies significantly between sea cucumbers species. Total As in studied body parts ranged between 2.8 ± 0.52 and 7.9 ± 1.2 mg kg-1, with an exception of the muscle tissue of A. californicus, where it reached to 36 ± 3.5 mg kg-1. Arsenobetaine (AsB) was the most abundant As species in A. californicus and A.japonicus, however, inorganic As represented over 70% of total recovered As in the body parts of C. frondosa. Arsenosugars-328 and 482 were found in all studied body parts whereas arsenosugar-408 was only found in the skin of A. californicus. This is the first time that such a variation in As species distribution between sea cucumber species has been shown.