Status of Mercury and Other Heavy Metals in South African Marine Fish Species
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Status of mercury and other heavy metals in South African marine fish species Adina Cornelia Bosch Dissertation presented for the degree of Doctor of Philosophy (Food Science) in the Faculty of AgriSciences, Stellenbosch University Promoter: Prof Louwrens C. Hoffman Co-Promoters: Dr Gunnar O. Sigge; Prof Sven E. Kerwath & Dr Bernadette O’Neill December 2015 Stellenbosch University https://scholar.sun.ac.za Declaration By submitting this dissertation electronically, I declare that the entirety of the work contained therein is my own, original work, that I am the sole author thereof (save to the extent explicitly otherwise stated), that reproduction and publication thereof by Stellenbosch University will not infringe any third party rights and that I have not previously in its entirety or in part submitted it for obtaining any qualification. This dissertation includes three original papers published in peer-reviewed journals and books and five unpublished publications. The development and writing of the papers were the principle responsibility of myself and for each of the cases where this is not the case, a declaration is included in the dissertation indicating the nature and extent of the contribution of co-authors. Date: 17 August 2015 Copyright © 2015 Stellenbosch University All rights reserved ii Stellenbosch University https://scholar.sun.ac.za Acknowledgements I wish to thank, first of all, my supervisors Prof Louwrens Hoffman, Prof Sven Kerwath, Dr Gunnar Sigge and Dr Bernadette O’Neill for all the help and guidance throughout the entire PhD process, each in a unique way. Prof Hoffman, thank you for providing me opportunities to gain experiences I never even dreamt of having and which I will carry with me for the rest of my life and for guiding me into becoming a researcher through the love that you yourself have for research. To the multitude of friends, contacts and strangers who have helped me find the right contacts in the South Afrcan fishing community in order to obtain all the samples I needed. To the extended South African fishing community and all the fishermen who provided me with these samples, and even to those who tried unsuccessfully. You are almost too many to mention, but I would not have finished this study if it were not for all your help. The staff and fellow post-graduate students of the Department of Animal Sciences are thanked for their support and assistance and Riana Rossouw (CAF) for her assistance and patience with the analytical work. To Professor Martin Kidd, for statistical analyses and expert advice; thank you. The authors wish to acknowledge use of the Maptool program (product of SEATURTLE.ORG. Information is available at www.seaturtle.org) for analysis and graphics in this dissertation. The National Research Foundation (NRF) is acknowledged for funding (any opinion, findings and conclusions or recommendations expressed in this material are those of the author(s) and therefore the NRF does not accept any liability in regard thereto). Then to my family for the continuous humour as well as support, advice, prayers, care and love; to all my friends and extended ‘family’ for always showing interest in what I do and believing in me more than I sometimes did myself; fellow PhD’s for understanding and mostly knowing which questions not to ask. To my fiancé, David, for celebrating every small victory with me and helping me to enjoy this journey till the end. Finally I wish to thank my heaveny Father from whom comes my every ability and all my joy and peace through His grace. iii Stellenbosch University https://scholar.sun.ac.za Notes This thesis is presented in the format prescribed by the Department of Food Science, Stellenbosch University. The structure is in the form of one or more research chapters (papers prepared for publication) and is prefaced by an introduction chapter with the study objectives, followed by a literature review chapter and culminating with a chapter for elaborating a general discussion and conclusions. Language, style and referencing format used are in accordance with the requirements of the International Journal of Food Science and Technology. This thesis represents a compilation of manuscripts where each chapter is an individual entity and some repetition between chapters has, therefore, been unavoidable. Results from this dissertation that have been published in the following journals: Bosch, A. C., O’Neill, B., Sigge, G. O., Kerwath, S. E., & Hoffman, L. C. (2016). Heavy metal accumulation and toxicity in smoothhound (Mustelus mustelus) shark from Langebaan Lagoon, South Africa. Food Chemistry, 190, 871–878. Bosch, A. C., O’Neill, B., Sigge, G. O., Kerwath, S. E., & Hoffman, L. C. (2016). Mercury accumulation in Yellowfin tuna (Thunnus albacares) with regards to muscle type, muscle position and fish size. Food Chemistry, 190, 351–356. Bosch, A. C., O’Neill, B., Sigge, G. O., Kerwath, S. E., & Hoffman, L. C. (Accepted for publication). Heavy metals in marine fish meat and consumer health: A review. Journal of the Science of Food and Agriculture. Results from this dissertation that have been presented at the following conferences: Bosch, A. C., O’Neill, B., Sigge, G. O., Kerwath, S. E., & Hoffman, L. C. (2014). Evaluation of mercury accumulation in Yellowfin tuna (Thunnus albacares) muscle with regards to muscle type and muscle position. 15th Southern African Marine Science Symposium, Stellenbosch, South Africa; 15-18 July 2014. Oral presentation. iv Stellenbosch University https://scholar.sun.ac.za Summary Fish is an important food source in South Africa as it is globally, thus the importance of determining and monitoring its safety in terms of metal contaminants and consumer safety. Effective methodology for analysing total metal concentrations and toxic metal components together with representative sampling protocol for sampling individual fish and larger catches are therefore required for accurate assessment of meat safety. Both inductively coupled plasma mass spectrometry (ICP-MS) and high pressure liquid chromatography coupled to ICP-MS was validated as effective methods for accurately determining concentrations of total metals and individual Hg species, respectively. Consequently, it was found that total mercury loads in fish meat consisted mainly of toxic methylmercury (MeHg) components with a minor addition of an inorganic Hg (iHg) component and ethylmercury concentrations being negligible. This proportion of MeHg to iHg varied between muscle types in yellowfin tuna (Thunnus albacares), with higher iHg concentrations in dark muscle than in white muscle, whereas the toxic MeHg concentrations did not vary across the carcass. The MeHg to tHg relationship was caused to vary with variation in fish weight, being described by the following prediction model: 푐푀푒퐻푔 = 0.073 + 1.365 ∙ 푐푡퐻푔 − 0.008 ∙ 푤; taking into account fish weight as covariate. For the eight other fish species studied [blacktail (Diplodus sargus capensis), hottentot (Pachymetopon blochii), yellowtail (Seriola lalandi), snoek (Thyrsites atun), blue shark (Prionace glauca), shortfin mako (Isurus oxyrinchus), soupfin (Galeorhinus galeus) and smoothhound (Mustelus mustelus)], the relationships between MeHg and tHg were constant even with varying fish sizes as iHg components were considered an insignificant portion of tHg (ctHg = cMeHg). The tHg measurements could therefore be used as accurate indicators of MeHg concentrations without requiring addition speciation analyses. Sampling from the cephalic region of the dorsal white muscle tissue proves representative of the entire edible portions (white muscle) of larger fish (tuna and sharks spp.) for determining both total metal concentrations and toxic Hg components. Where Hg concentrations are positively correlated to fish size (yellowfin tuna, yellowtail and soupfin), subsamples should include individuals representing the entire size range present per catch. A summary of metal concentrations in all eight species studied indicate that Hg is the main metal of concern where a single portion of certain fish (yellowfin tuna, shortfin mako, soupfin and smoothhound shark) consumed per week could exceed regulatory limits for safe Hg intake, whereas other fish species (hottentot) could be consumed daily without concern of Hg toxicity. Information provided by this study will prove useful to both the fishing and processing industry as well as to health authorities providing information for dietary exposure assessments. v Stellenbosch University https://scholar.sun.ac.za Opsomming Vis word gesien as ‘n belangrike voedsel bron in Suid-Afrika sowel as globaal en die bepaling en monitering van visveiligheid in terme van metaal kontaminasie is dus van uiterse belang. Effektiewe metodes vir die analise van totale-metaal konsentrasies en protokol vir verteenwoordigende steekproefneming van enkele visse sowel as van groter vangste is dus belangrik vir die akkurate bepaling van voedselveiligheid in die visbedryf. Beide ICP-MS en HPLC-ICP-MS is onderskeidelik gevalideer as effektiewe metodes vir die akkurate bepaling van totale-metaal konsentrasies en indiwiduele kwik (Hg) spesies. Gevolglik is daar gevind dat totale Hg ladings grootliks bestaan uit metiel-kwik (MeHg) met kleiner bydraes van anorganiese kwik (iHg). Die bydrae van etiel-kwik (EthHg) is egter nietig bevind. Die proporsie MeHg tot iHg het verskil tussen spier-tipes in geelvin tuna (Thunnus albacares) met hoër iHg konsentrasies in die donker spier as in die ligte spier. Die konsentrasies van toksiese MeHg