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New arsenic compounds found in herring


While arsenic sometimes is used as a synonym for poison, today because of its easy detectability, arsenic is less interesting as an "assassin's poison", but it is still a problem in food. Arsenic enters the environment and thus the food chain from volcanic eruptions, combustion of fossil fuels and also through groundwater. But actually how big is the risk from arsenic in food? Are arsenic-containing compounds absorbed by the human body and possibly converted into more toxic forms? So far, very little is known about this.

The new study:

Picture: Atlantic herring
To address these issues, chemists of the BAM Federal Institute for Materials Research and Testing have investigated herring fillets for arsenic and various arsenic compounds in cooperation with the Helmholtz Centre for Environmental Research (UFZ) in Leipzig.

So far interest has mainly been directed towards the total arsenic content. "The total arsenic content in food, however, does not say anything about the effect arsenic may have on the human body. For each arsenic-containing compound has a different toxicological significance", says BAM's Christian Piechotta. Therefore, extensive analyses have been performed to identify arsenic-containing compounds in herring.

Food is routinely analysed quantitatively for certain, and therefore known, ingredients within food control. However standardised methods for the analysis of individual arsenic compounds in food are not yet available.

"The difficult thing about our study is that we do not know exactly what compounds to look for, accordingly the analysis method must be comprehensive", says Susanne Lischka, who, together with Christian Piechotta, has conducted and reported the tests in the journal "Talanta" (see below). Frozen herring fillets from the supermarket were peeled, chopped and freeze-dried to remove the high water content in the fish - then ground, homogenised and dried again.

"This extent of sample preparation is necessary to ensure that we have a homogeneous material", says Piechotta. The scientists believe that this is not a conventional food analysis, rather a comprehensive speciation analysis, which needs to detect all chemical compounds of an element which occur in the sample.


Figure: new arsenolipids found in herring

Thus 18 arsenic compounds have been clearly characterised and amongst them, seven new arsenolipids (see figure left) are described for the first time. Arsenolipids are fat-soluble arsenic compounds. They are produced naturally by fish, but their effect on the human body has so far been unexplored.

"Our results are the fundamentals for toxicologists. They can only assess their health risks when the various arsenic compounds have been clearly identified in the herring and the human body", says Lischka.

It is known that the human body can metabolise arsenolipids. Back in 2006, Austrian scientists in Prof. Ernst Schmeisser's working group found that panellists who had been given arsenic-containing cod liver to eat, later had specific arsenolipids in their urine that had not previously been detected in the cod liver. Over the long term, BAM scientists want to synthesise individual arsenic compounds in the laboratory in order to provide reference materials which can then be used in food analysis laboratories to search for these arsenic compounds - for prophylaxis to keep fish as a healthy food.

Source: Adapted from BAM

The original study:

S. Lischka, U. Arroyo-Abad, J. Mattusch, A. Kühn, Ch. Piechotta, The high diversity of arsenolipids in herring fillet (Clupea harengus), Talanta, 110 (2013) 144-152. doi: 10.1016/j.talanta.2013.02.051

Related studies (newest first):

Uriel Arroyo-Abad, Susanne Lischka, Christian Piechotta, Jürgen Mattusch, Thorsten Reemtsma, Determination and identification of hydrophilic and hydrophobic arsenic species in methanol extract of fresh cod liver by RP-HPLC with simultaneous ICP-MS and ESI-Q-TOF-MS detection, Food Chem., 141/3 (2013) 3093-3102. doi: 10.1016/j.foodchem.2013.05.152

Veronika Sele, Heidi Amlund, Marc H.G. Berntssen, Jannicke A. Berntsen, Kasper Skov, Jens J. Sloth, Detection of arsenic-containing hydrocarbons in a range of commercial fish oils by GC-ICPMS analysis, Anal. Bioanal. Chem., 405 (2013) 5179–5190. DOI: 10.1007/s00216-013-6925-y

Maria Jose Ruiz-Chancho, Mojtaba S. Taleshi, Walter Goessler, Kevin A. Francesconi, A method for screening arsenolipids in fish oils by HPLC-ICPMS, J. Anal. At. Spectrom., 27 (2012) 501-504. DOI: 10.1039/c1ja10260e

Veronika Sele, Jens J. Sloth, Anne-Katrine Lundebye, Erik H. Larsen, Marc H.G. Berntssen, Heidi Amlund, Arsenolipids in marine oils and fats: A review of occurrence, chemistry and future research needs, Food Chem. , 133 (2012) 618–630. doi: 10.1016/j.foodchem.2012.02.004

Kenneth O. Amayo, Asta Petursdottir, Chris Newcombe, Helga Gunnlaugsdottir, Andrea Raab, Eva M. Krupp, Jörg Feldmann, Identification and Quantification of Arsenolipids Using
Reversed-Phase HPLC Coupled Simultaneously to High-Resolution ICPMS and High-Resolution Electrospray MS without Species-Specific Standards
, Anal. Chem., 83 (2011) 3589–3595. doi: 10.1021/ac2005873

Uriel Arroyo-Abada, Jürgen Mattusch, Sibylle Mothes, Monika Moder, Rainer Wennrich, Maria P. Elizalde-Gonzalez, Frank-Michael Matysik, Detection of arsenic-containing hydrocarbons in canned cod liver tissue, Talanta, 82 (2010) 38–43. doi: 10.1016/j.talanta.2010.03.054

M.S. Taleshi, J.S. Edmonds,  W. Goessler, G. Raber, Kenneth B. Jensen, K.A. Francesconi, Arsenic-Containing Lipids Are Natural Constituents of Sashimi Tuna, Environ. Sci. Technol., 44 (2010) 1478–1483. doi: 10.1021/es9030358

Georg Raber, Reingard Raml, Walter Goessler and Kevin A. Francesconi, Quantitative speciation of arsenic compounds when using organic solvent gradients in HPLC-ICPMS, J. Anal. At. Spectrom., 25 (2010) 570–576. DOI: 10.1039/b921881e

Alice Rumpler, John S. Edmonds, Mariko Katsu, Kenneth B. Jensen, Walter Goessler, Georg Raber, Helga Gunnlaugsdottir, and Kevin A. Francesconi, Arsenic-Containing Long-Chain Fatty Acids in Cod-Liver Oil: A Result of Biosynthetic Infidelity?, Angew. Chem. Int. Ed. 2008, 47, 2665 –2667. DOI: 10.1002/anie.200705405

Mojtaba S. Taleshi, Kenneth B. Jensen, Georg Raber, John S. Edmonds, Helga Gunnlaugsdottir, Kevin A. Francesconi, Arsenic-containing hydrocarbons: natural compounds in oil from the fish capelin, Mallotus villosus, Chem. Commun., 39 (2008) 4706–4707. DOI: 10.1039/b808049f

Ernst Schmeisser, Alice Rumpler, Manfred Kollroser, Gerald Rechberger, Walter Goessler, Kevin A. Francesconi, Arsenic Fatty Acids Are Human Urinary Metabolites of Arsenolipids Present in Cod Liver, Angew. Chem. Int. Ed., 45 (2006) 150–154. DOI: 10.1002/anie.200502706

Ernst Schmeisser, Walter Goessler, Kevin A. Francesconi, Human metabolism of arsenolipids present in cod liver, Anal. Bioanal. Chem., 385 (2006) 367–376. DOI 10.1007/s00216-006-0401-x

Ernst Schmeisser, Walter Goessler, Norbert Kienzl and Kevin A. Francesconi, Direct measurement of lipid-soluble arsenic species in biological samples with HPLC-ICPMS, Analyst, 130 (2005) 948–955. DOI: 10.1039/b502445e.

Valery M. Dembitsky, Dmitrii O. Levitsky, Arsenolipids, Progress in Lipid Research, 43 (2004) 403–448. doi:10.1016/j.plipres.2004.07.001

Mariko Miyajima, Noriaki Hamada, Etsuro Yoshimura, Akira Okubo, Sunao Yamazaki, Shozo Toda, Lipophilic arsenic compound(s) in the liver of a tiger shark (Galeocerdo cuvier), Appl. Organomet. Chem., 2 (1988) 377-384. doi: 10.1002/aoc.590020416

G. Lunde, Analysis of Arsenic in Marine Oils by Neutron Activation. Evidence of Arseno Organic Compounds, J. Am. Oil Chem. Soc., 45 (1968) 331-332. DOI: 10.1007/BF02667103

Related EVISA Resources

Brief summary: Speciation and Toxicity
Brief summary: Standard methods for arsenic speciation analysis
Brief Summary: LC-ICP-MS: The most often used hyphenated system for speciation analysis
Link database: Toxicity of organic arsenic species
Link database: Toxicity of inorganic Arsenic
Link database: Human exposure from arsenic in the diet
Link database: Analytical Methods for Arsenic Speciation Analysis
Link Page: All about food science
Material Database: Materials for Arsenic speciation analysis

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last time modified: March 3, 2024


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