Introduction of Inorganic Elements and Element Speciations Research Works in Food Safety Metrology, NIM China. Da Nang, Vietnam 10 Nov.

Transcription

1 APEC Workshop for Food Safety Introduction of Inorganic Elements and Element Speciations Research Works in Food Safety Metrology, NIM China WEI Chao Food Safety Lab, Chemical Division, NIM Da Nang, Vietnam 10 Nov. 2016

2 Contents 1 Background 2 Main Work about Inorganic Elements 3 Main Work about Element Speciation 4 Future Prospect

3 Influence of Element & Speciation Legislation/ Litigation Medicines Food Humans Health/ Consumers Environment Trade and Industry

4 International Comparisons SI NIM CMCs Methods CRMs PTs Food Safety Testing Laboratory in China

5 Food Matrix CRMs about Elements CRM No. Matrix Methods Elements and Speices GBW08509a GBW08521 GBW10029 Skimmed Milk Powder Laver Powder Fish Tissue Powder IDMS, IC, Kjeldahl, ICP-MS, ICP- OES, AFS, AAS IDMS, INAA, ICP-MS, ICP-OES, AFS, AAS IDMS, ICP-MS, AAS, ID-GC- ICPMS, ID-LC-ICPMS, HPLC- CVAFS Se, Zn, Fe, As, K, Na, Ca, Cu, Mn, Pb, Mg, N, P, Cl As, Pb, Cd Hg, MeHg GBW10035 Wheat Powder IDMS, ICP-MS, ICP-OES Pb, Cd, Cr GBW10036 Corn Powder IDMS, ICP-MS, ICP-OES Pb, Cd, Cr GBW10054 defatted soybean powder IDMS, ICP-MS, AAS, ICP-OES K,Mg,Ca,Fe,Zn,Mn,Cu,Na GBW10055 whole fat soybean powder IDMS, ICP-MS, AAS, ICP-OES K,Mg,Ca,Fe,Zn,Mn,Cu,Na GBW(E) Rice Powder AAS, ICP-OES, ICP-MS K, Mg, Ca, Fe, Mn, Zn, Cu, Na GBW(E) Wheat Powder AAS, ICP-OES, ICP-MS K, Mg, Ca, Fe, Mn, Zn, Cu, Na GBW(E) Corn Powder AAS, ICP-OES, ICP-MS K, Mg, Ca, Fe, Mn, Zn, Cu, Na GBW(E) Bovine Muscle Powder AAS, ICP-OES, ICP-MS K, Mg, Ca, Fe, Mn, Zn, Cu, Na GBW(E) Egg Yolk Powder AAS, ICP-OES, ICP-MS K, Mg, Ca, Fe, Mn, Zn, Cu, Na GBW(E) Cushaw Powder AAS, ICP-OES, ICP-MS K, Mg, Ca, Fe, Mn, Zn, Cu, Na GBW(E) Infant Formula ICP-MS, ICP-OES, AAS, XRF, SP Se, Zn, Fe, K, Na, Ca, Cu, Mn, Mg, P

6 Some New Issues of Food Safety in China

7 10 Elements Concent in Milk Powder CRM Infant Formula (low Background) Al, As, Cd, Cr, Cu, Hg, I, Ni, Pb, Se STD Solution Spray drying

8 Conc.(mg/kg) 10 Elements Concent in Milk Powder CRM IDMS Characterization A 1C 1D 4C 5C 6C 7C 8C 9F Methods & Lab Code

9 Aluminum in Vermicelli CRM Normal Vermicelli Al: 4mg/kg Spiked Vermicelli Al: ~300mg/kg Ultra Centrifugal Mill blending machine Jet Mill

10 Chromium in Gelatine CRM Blending Milling Industrial gelatin (Cr>100mg/kg) Mixing and dissolving Medicinal gelatin Cr<0.3mg/kg) Cutting Drying Cooling

11 International Comparisons about Element in Food- CCQM/IAWG Reference No. Description Start date CCQM-K24 Cd in Rice 2001 CCQM-K30 Pb in wine 2006 CCQM-K43.1 As, Hg, Se and methylmercury content in marine fish 2005 CCQM-K49 Toxic and essential elements in bovine liver 2006 CCQM-K56/P64.1 Trace elements in Soybean powder 2006 CCQM-K60 Total Se and Se speciation analysis of Se-rich wheat flour 2008 CCQM-K75 Toxic metals in algae 2009 CCQM-K89/P126 Trace and essential elements in Herba Ecliptae 2010 CCQM-K108/P147 Determination of arsenic species, total arsenic and cadmium in brown rice flour 2013 CCQM-K124/P158 Trace elements and chromium speciation in drinking water 2014 CCQM-K125/P159 Iodine and other elements in infant formula 2014 CCQM-P39 As, Se, Hg, Pb, methyl-hg in tuna fish 2003 CCQM-P64 Trace elements in soyabean powder 2004 CCQM-P86 Analysis of total Se and Se methionine in pharmaceutical supplements 2006 CCQM-P96 As and arsenobetaine content in marine fish 2007 CCQM-P96.1 As and arsenobetaine in calibration solution and Japanese sea bass sample 2010 CCQM-P97 Cd and Pb in Herb 2006

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14 International Comparisons about Elements in Food APMP & ACRM Reference No. Description Start date APMP-QM-P02 Cd in rice 2001 APMP-QM-K24/P12 Cd in rice 2005 APMP.QM-S5 Essential and toxic elements in seafood 2011 ACRM-01 Se,Zn,Hg in Tuna Fish 2006 ACRM-02 Methyl mercury in tuna fish 2006 ACRM-04 Rice flour (Cd, Cu, Zn) 2007 ACRM-07 Laver (Pb, As, Cd) 2008 ACRM-13 Milk powder CRM (Elements) 2010 ACRM-14 Tea leaf CRM (Elements) 2010 ACRM-22 Garlic CRM(Elements) 2014

15 APMP-QM-K24: Cd in Rice

16 ACRM action # 23 Garlic Powder CRM from KRISS

17 National Proficiency Tests Provided Year Name number of participants 2011 Determination of sodium thiocyanate in liquid milk Determination of lead and chromium in solution Determination of lead and chromium in milk powder Determination of lead and chromium in tea Determination of cadmium in rice Determination of aluminum in vermicelli Determination of lead, Chromium and mercury in milk powder Determination of Selenium and Ba in drinking water Cu, Se and protein content in infant formula milk powder Determination of Selenium and Ba in drinking water 60 Many of PT materials are converted to CRM later after stability tests.

18 PT - Lead in infant milk powder 144 labs Z 2: 93 2< Z 3 :13 Z >3 :33 No data reported:5

19 Research Work about Element Speciation Total element determination Element speciation

20 CCQM Comparisons about Element Speciation in Recent Years Time Code Analyte Matrix Pilot laboratory The number of participants 2005 CCQM P39.1 Methylmercury Salmonfish IRMM CCQM K43 Methylmercury Salmonfish IRMM CCQM P86 Selenomethionine Yeast LGC & NRCC CCQM K43.1 Methylmercury Swordfish NMIJ CCQM P96 Arsnobetaine Swordfish NMIJ & NIM CCQM K60 Selenomethionine Se-rich wheat flour LGC & NRCC CCQM P114 PBDE & PBB Plastic IRMM CCQM P96.1 Arsnobetaine Solution & Codfish NMIJ & NIM CCQM K97&P133 Arsnobetaine Solution & tunafish NIM & NMIJ CCQM-K108 Arsenic Species Rice NMIJ CCQM K Arsenic Species Rice NMIJ CCQM-K124 Chromium Species Drinking Water NMIJ/GLHK CCQM-K128 Organo-tin Leather NIM 5

21 Arsenic : LD 50 in rats (in mg/kg): Toxic Carcinogenic Stable & Safe

22 ) Arsenic Speciation Calibration Solutions Code GBW08666 GBW08667 GBW08668 GBW08669 GBW08670 GBW08671 Species Arsenite Arsenate Monomethylarsonic acid Dimethylarsenic acid Arsenobetaine Arsenocholine Conc.(μ mol/g Characterization - arsenite 0.99 Coulometer ICP-MS ICP-OES AFS HPLC- ICPMS

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24 mass fraction of AsB (mg/kg) Results of fish tissue: K97 & P Shape : ICPMS : MS K97 Fish tissue Each bar indicates the expanded unc. P133 Colour : LC/ext cal : LC/ID : LC/std add

25 Minamata disease

26 Mercury Speciation Calibration Solutions GBW(E) Ethylmercury in methanol GBW08675 Methylmercury in methanol

27 浓度 (mg/kg) Mercury Speciation Matrix CRMs 1 Methyl Mercury in Fish Tissue 0.9 GBW10029 Total Mercury and Methyl Mercury in Fish Tissue HPLC-CV-AFS ID-LC-ICPMS ID-GC-ICPMS Nankai University NIM NMIJ

28 SS-ID-LC-ICPMS ERM-AE MeHg A b u n d a n c e I o n ( t o ): H G S T D 1. D I o n ( t o ): H G S T D 1. D shaking extracting MeHg Hg Sample T im e --> HPLC Pump Column ICP-MS

29 CCQM K43 & K43.1 As, Hg, Se and methylmercury content in marine fish (swordfish)

30 Selenomethionine (SeMet)* 80 Se H 3 C C H 2 H 2 C H C O NH 2 OH -glutamyl-semc O H 2 N H O C H C H 2 C H 2 O H 3 C N H 80 Se H C H O Selenomethyl-Se-cysteine(SeMC)* C H 2 O Methylselenol (CH 3 SeH) H 3 C 80 Se H 2 C H C NH 2 O OH Selenite (SeO 3 2- ) Selenate (SeO 4 2- )

31 Selenium speciation Calibration solutions Code GBW10032 GBW10033 GBW10034 GBW10087 GBW10088 Se Species Selenite Selenate Selenomethionine Seleno-Cystine (Methyl) Seleno-Cysteine 0.6 Characterization - selenite Conc. ( μ mol/g ) ICP - MS IDMS HPLC ICPMS ICP-OES

32 CCQM K60 & P86.1 Analysis of Selenomethionine in wheat flour USC UME NMISA BAM HillLab USDA NRCC PTB Ugraz LGC NMIA LNE NMIJ NIM CUBud NFI/TUD CUM CISTA UMASS HSA INTI UH

33 Tin Speciation Calibration Solution GBW08710 TBT in methanol GBW08711 DBT in methanol GBW08712 TPhT in methanol

34 Organo-Sn in Oyster CRM GBW10068

35 Organo-tin in Leather (In progress) Sample prepared (tributyl-tin was spiked during production of leather), homogeneity tested, 6 months stability tested, characterization and longer term stability test in progress Low Conc. (~100mg/kg) High Conc. (~1000mg/kg)

36 CMCs about Element Speciation

37 Future Prospect CRMs for arsenic species in food Inorganic arsenic species in rice Arsenobetaine in fish Arsenosugars in seaweed CRMs for arsenic species in feeds Roxarsone in chicken feed Arsanilic acid in pig feed CRMs for Selenium and Chromium Species in food supplement SeMet, Se-Cys, inorg-se in Se-enriched food Cr3+ and Cr 6+ in food supplement

38 Colleagues

39 Questions? More detail information about CRMs, Please visit: