Determination of Chlorinated Endocrine Disrupting Chemicals in Lamb Tissues by Gas Chromatography Mass Spectrometry and Effects of Gender

Abstract

The history of endocrine disrupting chemicals that alter the synthesis/degradation of natural hormones by binding or activating endocrine receptors in the body goes back to the 1950s. Organochlorine pesticides (OCP), Polichlorinated biphenyls (PCBs) and Polybrominated diphenyl ethers (PBDEs), which are currently banned but are used extensively for a period, remain in nature for a long time due to their high stability and oil deposition properties. Due to bioaccumulation and biomagnification, the amounts are constantly increasing after entering the food chain. People's exposure (90%) to these chemicals comes from foods. We investigated the contamination of 14 OCPs (α, β, γ-hexachlorocyclohexane, hexachlorobenzene, 4,4'-dichlorodiphenyl dichloroethane,4,4'-dichlorodiphenyl dichloroethylene, 2,4’-dichloro diphenyl trichloroethane, 4,4’-dichloro diphenyl trichloroethane, heptachlor, aldrin, dieldrin, α-endosulfan, β-endosulfan, methoxychlor), 7 PCBs (28, 30, 52, 101, 118, 138, 153, 180) and 6 PBDEs (17, 47, 66, 100, 153, 183) in lamb meat and fat and the effect of sex on their levels. The method used was validated according to SANCO 12571/2013 and EUROCHEM 2014 Verification Manual. Endocrine disrupting chemicals residues were found in 75% of males and 33.3% of females samples. The residual contents of the PCBs detected in all of the samples. While hexachlorobenzene, 4,4’-dichloro diphenyl trichloroethane and PCB52 were the most common residues among the their groups, whereas only PBDE17 was detected in the PBDEs. Although the incidence of residues is higher in the male animals, the detected amount is higher in the female animals. All residues levels found below the level specified The Turkish Food Codex and The European Union Regulations. 

Keywords

• Endocrine disrupting chemical,PBDE,PCB,organochlorine pesticides,GC-MS,lamb meat

Kuzu Dokularında Endokrin Bozucu Klorlu Kimyasal Varlığının Gaz Kromatografi Kütle Spektrometrisi ile Saptanması ve Cinsiyetin Etkisi

Abstract

Vücuttaki endokrin reseptörlerine bağlanıp bunları aktive veya bloke ederek doğal hormonların sentez/parçalanmasını değiştiren endokrin bozucu kimyasallarla ilgili çalışmaların geçmişi 1950’li yıllara kadar gitmektedir. Günümüzde yasaklı olan ama bir dönem yoğun olarak kullanılan organik klorlu pestisitler (OCP), poliklorlu bifeniller (PCB) ve polibromlu difenileterler (PBDE) stabilitelerinin yüksek olması ve yağda birikme özellikleri nedeniyle doğada uzun süre kalmaktadırlar. Biyoakümülasyon ve biyomagnifikasyon nedeniyle gıda zincirine girdikten sonra miktarları sürekli artmaktadır. İnsanların bu kimyasallara maruziyetinin %90’ı bulaşık gıdalarla olmaktadır. Bu çalışmada 14 OCP (α, β, γ-hekzaklorosiklohekzan, hekzaklorobenzen, 4,4’-diklorodifenil dikloroetan, 4,4’-diklorodifenil dikloroetilen, 2,4’-diklorodifenil trikloroetan, 4,4’-diklorodifenil trikloroetan, heptaklor, aldrin, dieldrin, α-endosülfan, β-endosülfan, metoksiklor), 7 PCB (28, 30, 52, 101, 118, 138, 153, 180) ve 6 PBDE (17, 47, 66, 100, 153, 183)’in kuzu eti ve yağındaki miktarları ve cinsiyetin buna olan etkisi araştırılmıştır. Kullanılan yöntem SANCO 12571/2013 ve EUROCHEM 2014 Validasyon Kılavuzu’na göre valide edilmiştir. Toplamda erkek hayvanlara ait örneklerin %75’inde, dişilerinkinin ise %33.3’ünde endokrin bozucu kimyasal kalıntısına rastlanmıştır. Araştırılan örneklerin tamamında PCB tespit edilmiştir. Hekzaklorosiklohekzen ve 4,4’-diklorodifenil trikloroetan ile PCB52 kendi grupları içinde en sık rastlanılan kimyasallar olurken PBDE’lerden sadece PBDE17 tespit edilmiştir. Kalıntı görülme sıklığı erkeklerde daha fazla iken tespit edilen miktarların dişi hayvanlara ait örneklerde daha yüksek olduğu görülmüştür. Bulunan tüm kalıntıların seviyeleri Türk Gıda Kodeksi ve Avrupa Birliği’nin ilgili yönetmeliklerinde belirtilen seviyelerin altındadır.

Keywords

• Endokrin bozucu kimyasal,PBDE,PCB,organik klorlu pestisitler,GC-MS,kuzu eti

References

1. 1. Kavlock RJ, Daston GP, DeRosa C, et al. Research needs for the assessment of health and environmental effectsof endocrine disruptors: a report of the U.S. EPA-sponsored workshop. Environ Health Perspect. 1996;104(4):715-740.
2. 2. Zoeller RT, Brown TR, Doan LL, et al. Endocrine-disrupting chemicals and public health protection: a statement of principles from The Endocrine Society. Endocrinology. 2012;153(9):4097-4110.
3. 3. La Guardia MJ, Hale RC, Harvey E. Detailed polybrominated diphenyl ether (PBDE) congener composition of the widely used penta-, octa-, and deca-PBDE technical flame-retardant mixtures. Environmental Science and Technologie. 2006;40: 6247-6254.
4. 4. Grimm FA, Hu D, Kania-Korwel I, et al. Metabolism and Metabolites of Polychlorinated Biphenyls. Crit Rev Toxicol. 2015;45(3): 245-272.
5. 5. Jayaraj R, Megha P, Sreedev P. Organochlorine pesticides, their toxic effects on living organisms and their fate in the environment. Interdiscip Toxicol. 2016:9(3-4): 90-100.
6. 6. Ogata Y, Takada H, Mizukawa K, Hirai H, Iwasa S, Endo S, et al. International pellet watch: global monitoring of persistent organic pollutants (POPs) in coastal waters. 1. Initial phase data on PCBs, DDTs, and HCHs. Mar Pollut Bull. 2009;58(10):1437-1446.
7. 7. Okkerman PC, Van der Putte I. Endocrine disrupters: study on gathering information on 435 substances with insufficient data. Delft: RPS BKH Consultants BV 2002; 279.
8. 8. Stoytcheva M. Role of Pesticides in Human Life in the Modern Age: A Review. In: Saeedi Saravi, S.S. & Shokrzadeh, M, ed. Pesticides in the Modern World - Risks and Benefits. 1st ed. Intech open Access; 2011:1-21.

9. 9. Solecki R, Kortenkamp A, Bergman Å, et al. Scientific principles for the identification of endocrine-disrupting chemicals: a consensus statement. Arch Toxicol. 2017; 91(2): 1001-1006.
10. 10. WHO (2013). Ed. Bergman A, Heindel JJ, Jobling S, et al. Endocrine Disrupting Chemicals (EDCs). https://www.who.int/ceh/risks/cehemerging2/en/. (03.01.2019).
11. 11. Darnerud PO, Atuma S, Aune M, et al. Dietary intake estimations of organohalogen contaminants (dioxins, PCB, PBDE and chlorinated pesticides, eg DDT) based on Swedish market basket data. Food Chem Toxicol. 2006;44(9):1597-1606.
12. 12. Schwarz MA, Lindtner O, Blume K, et al. Dioxin and dl-PCB exposure from food: the German LExUKon project. Food Addit Contam Part A Chem Anal Control Expo Risk Assess. 2014;31(4):688-702.
13. 13. Kim M, Kim DG, Bong YH, et al. Concentrations of PCDD/Fs, dioxin-like PCBs, PBDEs, and hexachlorobenzene in fat samples from cattle of different ages and gender in Korea. Food Chem X. 2013;138(2-3):1786-1791.
14. 14. Covaci A, Voorspoels S, Roosens L, et al. Polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in human liver and adipose tissue samples from Belgium. Chemosphere. 2008;73(2):170-175.
15. 15. Kuzukiran O, Yurdakok-Dikmen B, Sevin S, et al. Determination of selected endocrine disruptors in organic, free-range, and battery-produced hen eggs and risk assessment. Environ Sci Pollut Res Int. 2018;25(35):35376-35386.
16. 16. Magnusson B, Ornemark U. Eurachem guide: The Fitness for Purpose of Analytical Methods-a Laboratory Guide to Method Validation and Related Topics. 2nd ed. Eurachem; 2014:57.
17. 17. R Core Team (2014). R: A language and environment for statistical computing. R Foundation for Statistical Computing, Vienna, Austria. http://www.R-project.org/ (18.08.2019).
18. 18. Wickham H. ggplot2: elegant graphics for data analysis. Springer New York 2009.
19. 19. Aguilar A. Relationship of DDE/ΣDDT in marine mammals to the chronology of DDT input into the ecosystem. Can J Fish Aquat Sci. 1984;41(6):840-844.
20. 20. Noël M, Loseto LL, Stern G. Legacy contaminants in the eastern Beaufort Sea beluga whales (Delphinapterus leucas): are temporal trends reflecting regulations? Arct Sci. 2018;4(3):373-387.
21. 21. Han L, Sapozhnikova Y, Lehotay SJ. Method validation for 243 pesticides and environmental contaminants in meats and poultry by tandem mass spectrometry coupled to low-pressure gas chromatography and ultrahigh-performance liquid chromatography. Food Control. 2016;66:270-282.
22. 22. Pine O, Nuro A. Organochlorine pesticides and PCB in meat and by-products from Albanian markets. Int. J. Environ. Sci. 2016;11(4):401-408.
23. 23. Yu YX, Huang NB, Zhang XY, et al. Polybrominated diphenyl ethers in food and associated human daily intake assessment considering bioaccessibility measured by simulated gastrointestinal digestion. Chemosphere. 2011;83(2):152-160.
24. 24. Huwe JK, West M. Polybrominated diphenyl ethers in US meat and poultry from two statistically designed surveys showing trends and levels from 2002 to 2008. J Agric Food Chem. 2011;59(10):5428-5434.
25. 25. Urbaniak M. Biodegradation of PCDDs/PCDFs and PCBs. In: Chamy R, Rosenkranz F editors. Biodegradation-Engineering and Technology. Croatia: InTech; 2014. p. 73-100.
26. 26. EFSA. Results of the monitoring of non dioxin-like PCBs in food and feed. EFSA Journal. 2010;8:1701.
27. 27. Gerecke AC, Hartmann PC, Heeb NV, et al. Anaerobic degradation of decabromodiphenyl ether. Environ Sci Technol. 2005;39(4):1078-1083.
28. 28. TGK. Türk Gıda Kodeksi Pestisitlerin Maksimum Kalıntı Limitleri Yönetmeliği. 29899 sayılı Resmi Gazete. 2016.
29. 29. EU 149/2008. Amending Regulation (EC) No 396/2005 of the European Parliament and of the Council by establishing Annexes II, III and IV setting maximum residue levels for products covered by Annex I thereto. 2008.
30. 30. TGK. Türk Gıda Kodeksi Bulaşanlar Yönetmeliği. 28157 sayılı Resmi Gazete. 2011.
31. 31. EU 1259/2011. Amending Regulation (EC) No 1881/2006 as regards maximum levels for dioxins, dioxin-like PCBs and non dioxin-like PCBs in foodstuffs. 2011.
32. 32. TGK. 2015/32 sayılı “Türk Gıda Kodeksi Belirli Gıdalarda Dioksinlerin, Dioksin Benzeri Poliklorlu Bifenillerin ve Dioksin Benzeri Olmayan Poliklorlu Bifenillerin Seviyesinin Resmi Kontrolü İçin Numune Alma, Numune Hazırlama ve Analiz Metodu Kriterleri Tebliği”, 29429 sayılı Resmi Gazete. 2015.
33. 33. EU 589/2014. Laying down methods of sampling and analysis for the control of levels of dioxins, dioxin-like PCBs and non-dioxin-like PCBs in certain foodstuffs and repealing Regulation (EU) No 252/2012. 2014.
34. 34. EU 1881/2006. Setting maximum levels for certain contaminants in foodstuffs. 2006.
35. 35. EPA 2017. Regional Screening Level (RSL) Summary Table. www.epa.gov/risk/regionalscreening-levels-rsls-generic-tables-may-2016.