Selective Quantification of Organic and Inorganic Arsenic in Kelp Thalli and Kelp-Based Products

Kelp can accumulate large quantities of arsenic compounds even in the absence of considerable environmental pollution. A substantial difference in toxicity between organic and inorganic arsenic compounds makes the form of arsenic relevant for the risk assessment of consuming kelp thalli and kelp-based products.

The aim of the study was to develop an analytical procedure for the selective quantification of organic and inorganic arsenic in kelp thalli by inductively coupled plasma mass spectrometry and solid-phase extraction without scheduled precursors.

Materials and methods. The authors studied samples of Laminaria saccharina and Laminaria japonica, spiking mixtures of chemical compounds containing arsenic in different oxidation states, and bioactive dietary supplements based on kelp thalli. Solid-phase extraction was performed using Maxi-Clean SAX cartridges. The arsenic content was determined using an Agilent 7900 inductively coupled plasma mass spectrometer.

Results. Microwave-assisted extraction with deionised water ensures 91% recovery of arsenic-containing compounds from kelp thalli, and the addition of hydrogen peroxide to the extractant provides complete extraction. Solid-phase extraction with an eluent based on 3% H2O2 can extract the organic fraction from a mixture of organic and inorganic arsenic compounds without washing the inorganic fraction off the cartridge.

Conclusions. The authors offer an effective analytical procedure for the selective quantification of organic and inorganic arsenic in kelp thalli and kelp-based products. This procedure allows for the isolation of arsenic-containing compounds from the organic matrix of kelp with 3% hydrogen peroxide. Solid-phase extraction with this extractant can effectively separate organic and inorganic fractions without prior neutralisation of the test solution.

1. Podkorytova AV, Roshchina AN. Marine brown algae — perspective source of BAS for medical, pharmaceu tical and food use. Trudy VNIRO. 2021;186(4):156–72 (In Russ.). https://doi.org/10.36038/2307-3497-2021-186-156-172

2. Semenova EV, Bilimenko AS, Chebotok VV. The use of seaweed in medicine and pharmacy. Modern Problems of Science and Education. 2019;(5):118 (In Russ.). EDN: OZNHEB

3. Choudhary B, Chauhan OP, Mishra A. Edible seaweeds: a potential novel source of bioactive metabolites and nutraceuticals with human health benefits. Front Mar Sci. 2021;8:740054. https://doi.org/10.3389/fmars.2021.740054

4. Podkorytova AV, Roshchina AN, Burova NV. Algaemacrophytes of the coastal zones of the seas of the northern fishery basin: harvesting, processing, justification of their integrated use. In: Innovative directions of integration of science, education and production. Kerch; 2020. P. 271–6 (In Russ.).

5. Wells ML, Potin P, Craigie JS, Raven JA, Merchant SS, Helliwell KE, et al. Algae as nutritional and functional food sources: revisiting our understanding. J Appl Phycol. 2017;29(2):949–82. https://doi.org/10.1007/s10811-016-0974-5

6. Obluchinskaya ED. Phytochemicals and technological study of the Barents Sea algae. Transactions of the Kola Science Centre. 2020;11(4–7):178–98 (In Russ.). https://doi.org/10.37614/2307-5252.2020.11.4.008

7. Shokina Y, Kuchina Y, Savkina K, Novozhilova E, Tatcienko K, Shokin G. The use of brown algae Laminaria saccharina in iodine enriched products aimed at preventing iodine deficiency. KnE Life Sci. 2022;2022:135–45. https://doi.org/10.18502/kls.v7i1.10115

8. Luvonga C, Rimmer CA, Yu LL, Lee SB. Organoarsenicals in seafood: occurrence, dietary exposure, toxicity, and risk assessment considerations — a review. J Agric Food Chem. 2020;68(4):943–60. https://doi.org/10.1021/acs.jafc.9b07532

9. Molin M, Ulven SM, Meltzer HM, Alexander J. Arsenic in the human food chain, biotransformation and toxicology — review focusing on seafood arsenic. J Trace Elem Med Biol. 2015;31:249–59. https://doi.org/10.1016/j.jtemb.2015.01.010

10. Zhao Y, Shang D, Ning J, Zhai Y. Arsenic and cadmium in the marine macroalgae (Porphyra yezoensis and Laminaria Japonica) — forms and concentrations. Chem Speciation Bioavailability. 2012;24(3):197–203. https://doi.org/10.3184/095422912X13404690516133

11. Monagail MM, Morrison L. Arsenic speciation in a variety of seaweeds and associated food products. Compr Anal Chem. 2019;85:267–310. https://doi.org/10.1016/bs.coac.2019.03.005

12. Kim M, Kim J, Noh CH, Choi S, Joo YS, Lee KW. Monitoring arsenic species content in seaweeds produced off the southern coast of Korea and its risk assessment. Environments. 2020;7(9):68. https://doi.org/10.3390/environments7090068

13. Khotimchenko SA, Bessonov VV, Bagryantseva OV, Gmoshinsky IV. Safety of food products: new problems and ways of solution. Occupational Medicine and Human Ecology. 2015;(4):7–14 (In Russ.). EDN: UWALFB

14. Bagryantseva OV, Khotimchenko SA. Risks associated with the consumption of inorganic and organic arsenic. Problems of Nutrition. 2021;90(6):6–17 (In Russ.). https://doi.org/10.33029/0042-8833-2021-90-6-6-17

15. Abramova LS, Gershunskaya VV, Kozin AV, Bondarenko DA, Murashev AN. Study of toxicity of arseniccontaining compounds isolated from the brown algae Saccharina japonica in laboratory animals. Trudy VNIRO. 2020;181:223–34 (In Russ.). https://doi.org/10.36038/2307-3497-2020-181-223-234

16. Banerjee M, Kaur G, Whitlock BD, Carew MW, Le XC, Leslie EM. Multidrug resistance protein 1 (MRP1/ABCC1)-mediated cellular protection and transport of methylated arsenic metabolites differs between human cell lines. Drug Metab Dispos. 2018;46(8):1096–105. https://doi.org/10.1124/dmd.117.079640

17. Bartel M, Ebert F, Leffers L, Karst U, Schwerdtle T. Toxicological characterization of the inorganic and organic arsenic metabolite Thio-DMAV in cultured human lung cells. J Toxicol. 2011;2011:373141. https://doi.org/10.1155/2011/373141

18. Leong F, Hua X, Wang M, Chen T, Song Y, Tu P, et al. Quality standard of traditional Chinese medicines: comparison between European Pharmacopoeia and Chinese Pharmacopoeia and recent advances. Chin Med. 2020;15(1):1–20. https://doi.org/10.1186/s13020-020-00357-3

19. Wrobel K, Wrobel K. Methodological aspects of speciation analysis in food products. In: De la Guardia M, Garrigues S, eds. Handbook of Mineral Elements in Food. John Wiley & Sons; 2015. P. 391–453. https://doi.org/10.1002/9781118654316.ch18

20. Hussam A, Alauddin M, Khan AH, Rasul SB, Mu nir AKM. Evaluation of arsine generation in arsenic field kit. Environ Sci Technol. 1999;33(20):3686–88. https://doi.org/10.1021/es9901462

21. Llorente-Mirandes T, Rubio R, López-Sánchez JF. Inorganic arsenic determination in food: a review of analytical proposals and quality assessment over the last six years. Appl Spectrosc. 2017;71(1):25–69. https://doi.org/10.1177/0003702816652374

22. López-García I, Briceño M, Hernández-Córdoba M. Non-chromatographic screening procedure for arse nic speciation analysis in fish-based baby foods by using electrothermal atomic absorption spectrometry. Anal Chim Acta. 2011;699(1):11–17. https://doi.org/10.1016/j.aca.2011.05.005

23. Raber G, Stock N, Hanel P, Murko M, Navratilova J, Francesconi KA. An improved HPLC–ICPMS method for determining inorganic arsenic in food: appli cation to rice, wheat and tuna fish. Food Chem. 2012;134(1):524–32. https://doi.org/10.1016/j.foodchem.2012.02.113

24. Cui S, Kim CK, Lee KS, Min HS, Lee JH. Study on the analytical method of arsenic species in marine samples by ion chromatography coupled with mass spectrometry. Microchem J. 2018;143:16–20. https://doi.org/10.1016/j.microc.2018.07.025

25. Santos CMM, Nunes MAG, Barbosa IS. Evaluation of microwave and ultrasound extraction procedures for arsenic speciation in bivalve mollusks by liquid chromatography — inductively coupled plasma-mass spectrometry. Spectrochim Acta, Part B: At Spectrosc. 2013;86:108–14. https://doi.org/10.1016/j.sab.2013.05.029

26. Pétursdóttir ÁH, Gunnlaugsdóttir H, Krupp EM, Feldmann J. Inorganic arsenic in seafood: does the extraction method matter? Food Chem. 2014;150:353–9. https://doi.org/10.1016/j.foodchem.2013.11.005

27. Rasmussen RR, Qian Y, Sloth JJ. SPE HG-AAS method for the determination of inorganic arsenic in rice — results from method validation studies and a survey on rice products. Anal Bioanal Chem. 2013;405(24):7851–7. https://doi.org/10.1007/s00216-013-6936-8

28. Kruglyakova US, Bagryantseva OV, Evstratova AD, Malinkin AD, Gmoshinskii IV, Khotimchenko SA. Separate quantitative determination of organic and non-organic arsenic in sea products. Health Risk Analysis. 2018;(2):112–8 (In Russ.). https://doi.org/10.21668/health.risk/2018.2.13

29. Rajaković LV, Todorović ŽN, Rajakovic-Ognjanovic VN, Onjia AE. Analytical methods for arsenic speciation analysis. J Serb Chem Soc. 2013;78(10):1461–79. https://doi.org/10.2298/JSC130315064R

30. Jinadasa KK, Peña-Vázquez E, Bermejo-Barrera P, Moreda-Piñeiro A. Ionic imprinted polymer solid phase extraction for inorganic arsenic selective pre-concentration in fishery products before high-performance liquid chromatography — inductively coupled plasma-mass spectrometry speciation. J Chromatogr A. 2020;1619:460973. https://doi.org/10.1016/j.chroma.2020.460973

31. Staniszewski B, Freimann P. A solid phase extrac tion procedure for the simultaneous determination of total inorganic arsenic and trace metals in seawater: sample preparation for total-reflection X-ray fluorescence. Spectrochim Acta, Part B: At Spectrosc. 2008;63(11):1333–7. https://doi.org/10.1016/j.sab.2008.08.018

32. Salgado SG, Nieto MAQ, Simon MMB. Determination of soluble toxic arsenic species in alga samples by microwave-assisted extraction and high performance liquid chromatography — hydride generation–inductively coupled plasma-atomic emission spectrometry. J Chromatogr A. 2006;1129(1):54–60. https://doi.org/10.1016/j.chroma.2006.06.083

33. Francesconi KA, Kuehnelt D. Determination of arsenic species: a critical review of methods and applications, 2000–2003. Analyst. 2004;129(5):373–95. https://doi.org/10.1039/B401321M