A group of Polish researchers investigated for the first time the arsenic speciation in honey samples.
Background:
Honey boasts invaluable nourishing, healing, and prophylactic properties rooted in its chemical composition. As a therapeutic foodstuff, honey must be devoid of hazardous compounds. Notably, honey serves as a marker for environmental pollution, with arsenic being a prominent concern due to its toxicity, varying significantly based on its species. This complexity underscores the necessity for speciation analysis to enable precise risk assessment.
The New Study:
Recently, researchers from Poland unveiled groundbreaking findings on arsenic concentration in honey samples collected from Poland and Ukraine, a pioneering endeavour in this domain. They devised a method to discern five arsenic species, including the highly toxic As(III), As(V), dimethylarsinic acid (DMA), methylarsonic acid (MMA), and the innocuous arsenobetain.
Their innovative separation technique, leveraging Ion Chromatography (IC) with gradient elution, coupled an anion exchange column with an anion–cation exchange guard column to enhance separation efficacy. The mobile phase, comprising ammonium nitrate and methanol, underwent pH adjustment with ammonia.
Honey samples underwent dilution with water and heated to 90°C for an hour to extract arsenic species, yielding high recovery values. Remarkably, total arsenic concentrations indicated the efficacy of water extraction.
Achieving separation of the five arsenic species within a concise timeframe of less than 14 minutes, the study unearthed predominantly inorganic arsenic species with varying As(III)/As(V) ratios contingent on the sampling region. Notably, MMA was solely detected in Ukrainian honey samples, while DMA featured in only one Polish honey sample.
However, the authors acknowledge their analysis solely addressed water-soluble arsenic, precluding direct comparison with existing results, given the absence of prior speciation data.
Comment:
An important consideration arises regarding the susceptibility of As(III) to oxidation to As(V) during sample preparation, particularly under elevated temperatures. Thus, the reliability of As(III)/As(V) ratios in honey samples post-heating to 80°C for an hour warrants scrutiny. Regrettably, the authors did not explore species stability under the conditions of their sample preparation, leaving this aspect unaddressed.
Michael Sperling
The original publication
Dorota Jakkielska, Marcin Frankowski, Anetta Zioła-Frankowska, Speciation analysis of arsenic in honey using HPLC-ICP-MS and health risk assessment of water-soluble arsenic, J. Hazard. Mater., 471 (2024) 134364. DOI: 10.1016/j.jhazmat.2024.134364
N.M. Zaric, S. Braeuer, W. Goessler, Arsenic speciation analysis in honey bees for environmental monitoring. J. Hazard. Mater., 432 (2022) 128614. DOI: 10.1016/j.jhazmat.2022.128614.
A. Mara, S. Deidda, M. Caredda, M. Ciulu, M. Deroma, E. Farinini, Multi-elemental analysis as a tool to ascertain the safety and the origin of beehive products: development, validation, and application of an ICP-MS method on four unifloral honeys produced in Sardinia, Italy. Molecules, 27/6 (2022) 2009. DOI: 10.3390/molecules27062009.
N. Altunay, A. Elik, M.F. Lanjwani, M. Tuzen, Assessment of arsenic in water, rice and honey samples using new and green vortex-assisted liquid phase microextraction procedure based on deep eutectic solvent: Multivariate study. Microchem. J., 179 (2022) 107541. DOI: 10.1016/j.microc.2022.107541.
N.H. Salman, L.M. Sam, K. Ador, B. Binjamin, M.I.J. Johny-Hasbulah, S. Benedick, Linking measure of the tropical stingless bee (Apidae, Meliponini, and Heterotrigona itama) honey quality with hives distance to the source of heavy metal pollution in urban and industrial areas in Sabah, Borneo. J. Toxicol., 2022 (2022) 4478082. DOI: 10.1155/2022/4478082.
Z. Sovrlic, S. Tosic, R. Kovacevic, V. Jovanovic, V. Krstic, The Importance of Measuring Arsenic in Honey, Water, and PM10 for Food Safety as an Environmental Study: Experience from the Mining and Metallurgical Districts of Bor, Serbia. Sustainability, 14 (2022) 12446. DOI: 10.3390/su141912446.
G. Di Bella, A.G. Potortì, A. Beltifa, H.B. Mansour, V. Nava, V. Lo Turco, Discrimination of Tunisian Honey by Mineral and Trace Element Chemometrics Profiling. Foods, 10/4 (2021) 724. DOI: 10.3390/foods10040724
G. Kastrati, M. Paçarizi, F. Sopaj, K. Tasev, T. Stafilov, M.K. Mustafa, Investigation of concentration and distribution of elements in three environmental compartments in the region of mitrovica, kosovo: soil, honey and bee pollen. Int. J. Environ. Res. Public Health, 18/5 (2021) 2269. DOI: 10.3390/ijerph18052269.
N.A. Obasi, C. Aloke, S.E. Obasi, A.C. Famurewa, P.N. Ogbu, G.N. Onyeji, Elemental composition and associated health risk of honey obtained from apiary farms in southeast Nigeria. J. Food Prot., 83/10 (2020) 1745–1756. DOI: 10.4315/JFP-20-072.
S. Squadrone, P. Brizio, C. Stella, S. Pederiva, F. Brusa, P. Mogliotti, Trace and rare earth elements in monofloral and multifloral honeys from Northwestern Italy; A first attempt of characterization by a multi-elemental profile. J. Trace Elem. Med. Biol., 61 (2020) 12655. DOI: 10.1016/j.jtemb.2020.126556.
S.S. Oliveira, C.N. Alves, E.S. Boa Morte, A.F. Santos Júnior, R.G.O. Araujo, D.C.M.B. Santos, Determination of essential and potentially toxic elements and their estimation of bioaccessibility in honeys. Microchem J., 151 (2019) 104221. DOI: 10.1016/j.microc.2019.104221.
D. Spiric, J. Ciric, V. Đorđevic, D. Nikolic, S. Jankovic, A. Nikolic, Toxic and essential element concentrations in different honey types. Int. J. Environ. Anal. Chem., 99/5 (2019) 474–485. DOI: 10.1080/03067319.2019.1593972
E.F. Fiorentini, B.V. Canizo, R.G. Wuilloud, Determination of As in honey samples by magnetic ionic liquid-based dispersive liquid-liquid microextraction and electrothermal atomic absorption spectrometry, Talanta, 198 (2019) 146-153. DOI: 10.1016/j.talanta.2019.01.091
O.E. Orisakwe, H.A. Ozoani, I.L. Nwaogazie, A.N. Ezejiofor, Probabilistic health risk assessment of heavy metals in honey, Manihot esculenta, and Vernonia amygdalina consumed in Enugu State, Nigeria. Environ. Monit. Assess., 191 (2019) 424. DOI: 10.1007/s10661-019-7549-2
H.I. Aljohar, H.M. Maher, J. Albaqami, M. Al-Mehaizie, R. Orfali, R. Orfali, Physical and chemical screening of honey samples available in the Saudi market: An important aspect in the authentication process and quality assessment. Saudi Pharm. J. 26/7 (2018) 932–942. DOI: 10.1016/j.jsps.2018.04.013.
Niki C. Maragou, George Pavlidis, Helen Karasali, Fani Hatjina, Determination of Arsenic in Honey, Propolis, Pollen, and Honey Bees by Microwave Digestion and Hydride Generation Flame Atomic Absorption, Anal. Lett., 50/11 (2017) 1831-1838. DOI: 10.1080/00032719.2016.1244542
Md. Solayman, A. Md. Islam, S. Paul, Y. Ali, I. Md. Khalil, N. Alam, Physicochemical properties, minerals, trace elements, and heavy metals in honey of different origins: a comprehensive review. Compr. Rev. Food Sci. Food Saf., 15/1 (2016) 219–233. DOI: 10.1111/1541-4337.12182.
N. Czipa, D. Andrási, B. Kovács, Determination of essential and toxic elements in Hungarian honeys. Food Chem., 175 (2015) 536–542. DOI: 10.1016/j.foodchem.2014.12.018.
H.M. Aghamirlou, M. Khadem, A. Rahmani, M. Sadeghian, A.H. Mahvi, A. Akbarzadeh, Heavy metals determination in honey samples using inductively coupled plasma-optical emission spectrometry. J. Environ. Health Sci. Eng., 13 (2015) 39. DOI: 10.1186/s40201-015-0189-8.
M. Moniruzzaman, M.A.Z. Chowdhury, M.A. Rahman, S.A. Sulaiman, S.H. Gan, Determination of mineral, trace element, and pesticide levels in honey samples originating from different regions of malaysia compared to manuka honey. Biomed. Res. Int., 2014 (2014) 359890. DOI: 10.1155/2014/359890.
J.M. Bastías, P. Jambon, O. Muñoz, N. Manquián, P. Bahamonde, M. Neira, Honey as a bioindicator of arsenic contamination due to volcanic and mining activities in Chile. Chil. J. Agric. Res. 73/2 (2013) 147–153. DOI: 10.4067/S0718-58392013000200010.
Q.-M. Ru, Q. Feng, J.-Z. He, Risk assessment of heavy metals in honey consumed in Zhejiang province, southeastern China. Food Chem Toxicol 53 (2013) 256–262. DOI: 10.1016/j.fct.2012.12.015.