Larsen, Erik Huusfeldt

Loeschner, Katrin

Sloth, Jens Jørgen

Trier, Xenia

Online Research Database In Technology

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Downloaded from orbit.dtu.dk on: Dec 20, 2017ICPMS as an element-specific detector for the analysis of trace element species andnanoparticlesSloth, Jens Jørgen; Trier, Xenia; Loeschner, Katrin; Larsen, Erik HuusfeldtPublication date:2012Document VersionPublisher's PDF, also known as Version of recordLink back to DTU OrbitCitation (APA):Sloth, J. J., Trier, X., Loeschner, K., & Larsen, E. H. (2012). ICPMS as an element-specific detector for theanalysis of trace element species and nanoparticles [Sound/Visual production (digital)]. Danish Society for MassSpectrometry Meeting 2012, Svendborg, Denmark, 01/01/2012, http://www.dsms.dk/ICPMS as an element-specific detector for the analysis of trace element species and nanoparticles Jens J. Sloth Xenia Trier, Katrin Loeschner and Erik H. Larsen  Inductively Coupled Plasma Mass Spectrometry ICPMS ICP-MS (Inductively coupled plasma mass spectrometry) is a type of mass spectrometry that is highly sensitive and capable of the determination of a range of metals and several non-metals at concentrations below one part in 1012 (ppt). It is based on coupling together an inductively coupled plasma as a method of producing ions (ionization) with a mass spectrometer as a method of separating and detecting the ions. ICP-MS is also capable of monitoring isotopic speciation for the ions of choice. Agilent ICPMS 7500ce Keywords: - High sensitivity - Multielement analysis - Isotopic speciation Mass spectrum – isotopic pattern of the elements ICPMS working range is from 6-250 m/z From lithium to uranium HPLC/GC Column ICPMS Result Sample introduction Separation Element specific detection Chromatogram Speciation analysis of elements Workhorse: HPLC-ICPMS (or GC-ICPMS) Output: Element-specific chromatogram 2.00 4.00 6.00 8.00 10.00 12.00      Time (min) Element conc (µg/kg) Different chemical forms of the element ••••••Example – arsenic speciation analysis Important for correct risk assessment 1 kg fish => 3000-10000 µg As 1 kg rice => 50-300 µg As There is most focus on rice from a food safety point of view – why??? The chemical form of arsenic is important => Arsenic speciation ~ 40 – 250 µg inorg As <10 µg inorg As 7 Arsenic compounds in the marine environment As O O H O H O H O H O H O H As As O O H O H C H 3 As O C H 3 O H C H 3 As O C H 3 C H 3 C H 3 C H 3 C H 3 C H 3 C H 3 As C H 3 C H 3 C H 2 C H 3 As C H 2 O H C H 3 C H 3 C H 2 C H 3 As C O O As O C H 3 C H 2 C H 3 C H 2 O H As O C H 3 C H 2 C H 3 C H 2 O H + + + - As(V) As(III) MA DMA TMAO TETRA AC AB DMAA DMAE OCH3CH2CH3As COOHTMAP O O P O O H O O H O H O H O O S O 3 H O H C O O H N H C O O H O R Dimethyl As-sugar 2 Dimethyl As-sugar 4 (7) (8) O OHOHO OPO OHOOHOH OHO SO3HOHO OSO3HOHO RAsOH OHOCH3CH3OMeOAsOH OHCH3CH3CH3RH COOHNHCOOHOAB2DimethylarsinoylribosideTrimethylarsonioribosideDimethyl As-sugar 1 Dimethyl As-sugar 2Dimethyl As-sugar 3 Dimethyl As-sugar 4+R = 1,2,3,4,5              (5) (6) (7)(8)More than 50 different arsenic species have been found in the marine environment As O O H O H O H O H O H O H As As O O H O H C H 3 As O C H 3 O H C H 3 As O C H 3 C H 3 C H 3 C H 3 C H 3 C H 3 C H 3 As C H 3 C H 3 C H 2 C H 3 As C H 2 O H C H 3 C H 3 C H 2 C H 3 As C O O As O C H 3 C H 2 C H 3 C H 2 O H As O C H 3 C H 2 C H 3 C H 2 O H + + + - As(V) As(III) MA DMA TMAO TETRA AC AB DMAA DMAE OCH3CH2CH3As COOHTMAP O O P O O H O O H O H O H O O S O 3 H O H C O O H N H C O O H O R Dimethyl As-sugar 2 Dimethyl As-sugar 4 (7) (8) O OHOHO OPO OHOOHOH OHO SO3HOHO OSO3HOHO RAsOH OHOCH3CH3OMeOAsOH OHCH3CH3CH3RH COOHNHCOOHOAB2DimethylarsinoylribosideTrimethylarsonioribosideDimethyl As-sugar 1 Dimethyl As-sugar 2Dimethyl As-sugar 3 Dimethyl As-sugar 4+R = 1,2,3,4,5              (5) (6) (7)(8)H OHOHAs AsOOHOHInorganic arsenic Arsenous acid As(III) Arsenic acid As(V) Arsenic compounds in the marine environment As O O H O H O H O H O H O H As As O O H O H C H 3 As O C H 3 O H C H 3 As O C H 3 C H 3 C H 3 C H 3 C H 3 C H 3 C H 3 As C H 3 C H 3 C H 2 C H 3 As C H 2 O H C H 3 C H 3 C H 2 C H 3 As C O O As O C H 3 C H 2 C H 3 C H 2 O H As O C H 3 C H 2 C H 3 C H 2 O H + + + - As(V) As(III) MA DMA TMAO TETRA AsC AB DMAA DMAE OCH3CH2CH3As COOHTMAP O O P O O H O O H O H O H O O S O 3 H O H C O O H N H C O O H O R Dimethyl As-sugar 2 Dimethyl As-sugar 4 (7) (8) O OHOHO OPO OHOOHOH OHO SO3HOHO OSO3HOHO RAsOH OHOCH3CH3OMeOAsOH OHCH3CH3CH3RH COOHNHCOOHOAB2DimethylarsinoylribosideTrimethylarsonioribosideDimethyl As-sugar 1 Dimethyl As-sugar 2Dimethyl As-sugar 3 Dimethyl As-sugar 4+R = 1,2,3,4,5              (5) (6) (7)(8)More than 25 different arsenic species have been found in the marine environment Organoarsenic compounds - trimethylated species Arsenocholine AC Arsenobetaine AB Trimethylarsoniopropionic acid TMAP CH3CH3CH2CH3As CH2OH+AsCH3CH3CH3 CH2CH2COOH+CH3CH3CH2CH3As COOH+Arsenic compounds in the marine environment As AB=”fish arsenic” 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.000100000200000300000400000500000600000700000800000900000100000011000001200000Time-->AbundanceIon  75.00 (74.70 to 75.70): 004SMPL.DTime (min) −> AB 11.00 12.00 13.00 14.00 15.00 16.00 17.00 18.00 19.00 20.00050010001500200025003000350040004500500055006000Time-->AbundanceIon  75.00 (74.70 to 75.70): 004SMPL.DTMAP TETRA TMAO AC Column: Chrompack Ionospher 5C; Mobile phase: Pyridine; pH = 2.7 Cation-exchange chromatogram of a MeOH/H2O extract of CRM DORM-2 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.000500100015002000250030003500400045005000Time-->AbundanceIon  75.00 (74.70 to 75.70): 004SMPL.DDMA DMAA Anions U Arsenic speciation in fish muscle by HPLC-ICPMS Sloth et al, J.Anal.Atom.Spectrom., 2003 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.005000100001500020000250003000035000400004500050000550006000065000Time-->   (   )  Signal intensity/ cps - seven compounds identified by coelution with available standards - 16 non-identified peaks Anions DMA DMAA AB AC TETRA TMAO TMAP ? ? ? ? ? ? ? ? ? ? ? ? ? ? Cation-exchange with gradient elution – extraction with aqueous methanol (50%) Column: Chrompack Ionospher 5C; Mobile phase: Pyridine; pH = 2.7 Speciation analysis of arsenic of scallop kidney Sloth et al, J.Anal.Atom.Spectrom., 2003 ? = unknowns (limitation of ICPMS detection) EFSA (2009) and JECFA (2010) opinions on arsenic in food  •NEW! BMDL1.0 = 0.3 – 8 µg/kg bw per day for inorganic arsenic •=> EU dietary exposures within this range for average and high level consumers •=> Risk to some consumers cannot be excluded  •NEW! BMDL0.5 = 3 µg/kg bw per day for inorganic arsenic •=> 0.5% increased incidence of lung cancer for 12 y exposure    “…there is a need to produce speciation data for different food commodities to support dietary exposure assessment…”  “…more accurate information on the inorganic arsenic content of foods is needed to improve assessments of dietary exposures to inorganic arsenic”  =>Risk assessments of dietary arsenic exposure  FOCUS ON INORGANIC ARSENIC                    Inorganic arsenic in wild caught fish => no concern Norwegian survey  900 individual fish samples   Atlantic halibut  Cod  Greenland halibut  Mackerel  Herring  Tusk  Results Total arsenic………..0.3-110 mg/kg  Inorganic arsenic…. < 0.01 mg/kg (only 37 samples > LOQ) Julshamn and Sloth, 2012, Fd Addit Contam, submitted iAs analysed by HPLC-ICPMS y = 0.51x - 1.51R2 = 0.9146012345670 2 4 6 8 10 12 14 16Total As / mg kg-1Inorganic As / mg kg-1Sloth and Julshamn, 2008, J. Agri.Food Chem., 56, 1269-1273 Data from 175 blue mussel (Mytilus edulis) samples collected along the Norwegian Coastline.  NORWAY Total As = 13.8 mg/kg Inorg As = 5.8 mg/kg Fraction = 42 % ...but in bivalves high contents in some samples...  iAs analysed by HPLC-ICPMS Arsenic in rice – an emerging health issue?   • 17 samples from supermarkets in Aberdeen • Total arsenic levels: 0.12 – 0.47 mg/kg • Inorganic arsenic: 0.06 – 0.16 mg/kg (33 – 69 % of tAs) • 35% above Chinese max level of 0.15 mg/kg iAs • 19 rice milk samples from supermarkets • EU drinking water ML: 10 µg/L total As (100% of samples exceeded) • US drinking water ML: 10 µg/L iAs (80% of samples exceeded) Arsenic in rice products DK - survey y = 0,8233x - 0,0099 R² = 0,863 0,000 0,100 0,200 0,300 0,400 0,500 0,600 0,00 0,10 0,20 0,30 0,40 0,50 0,60 0,70 Uorganisk As (mg/kg) Total As (mg/kg) iAs vs total As iAs vs total As Lineær (iAs vs total As) Chinese max level 0,15 mg/kg 105 samples -white rice -brown rice -red rice -black rice -rice crackers 33 samples > 0,15 mg/kg -2 parboiled (20%) -4 brown (50%) -4 red (50%) -5 black (71%) -1 Basmati (10%) -1 Pudding rice (9%) -1 wild rice (20%) -15 rice crackers (100%) Sloth et al, in prep iAs analysed by HPLC-ICPMS y = 0,8233x - 0,0099 R² = 0,863 0,000 0,100 0,200 0,300 0,400 0,500 0,600 0,00 0,10 0,20 0,30 0,40 0,50 0,60 0,70 Uorganisk As (mg/kg) Total As (mg/kg) iAs vs total As iAs vs total As Lineær (iAs vs total As) Future EU max level 0,2 mg/kg ?? 105 samples -white rice -brown rice -red rice -black rice -rice crackers Rice cracker mean: 0.31 mg/kg – intake 50 g/dag => 15 µg iAs (~1 µg/kg bw @15 kg bw) > EFSA BMDL01 0.3-8 µg/kg bw/dag 22 samples > 0,2 mg/kg -1 parboiled (10%) -1 brown (12%) -3 red (37%) -2 black (28%) -0 Basmati (0%) -0 Pudding rice (0%) -0 wild rice (0%) -15 rice crackers (100%) ? Sloth et al, in prep Arsenic in rice products DK - survey iAs analysed by HPLC-ICPMS Inorganic arsenic in chinese food supplements Hedegaard and Sloth, in prep Name of Food supplement Total Arsenic (μg/g) Inorganic arsenic  (μg/g ) Xiao Yao Wan 0.82 0.85 Bu Zhong Yi Qi Wan 0.62 0.50 Da Bu Yin Wan 0.59 0.55 Six Flavor teapills 0.72 N.D. Golden Book Teapills 0.58 0.57 Xiang Sha Liu Jun Zi Wan 0.94 0.80 Gan Mao Ling 1.24 1.01 Chuan Xin Lian 5.00 3.17 Bi Yan Pian 0.70 0.58 Arouse power 1.12 1.02 Bio Chlorella 0.62 0.21 Unik Spirulina Kapsler 2.59 0.13 Chlorella 0.58 0.03 Ez-Biloba 0.63 0.67 Qvinde Dong Quai 0.68 0.48 Gan Mao Ling (against flu and common cold)  Rec dose: 18 pills per day ⇒ iAs ~ 13 µg/day ⇒ 0.22 µg/kg bw/day (@60 kg) Close to EFSA BMDL01 !! an Mao Ling .  .  iAs analysed by HPLC-ICPMS Hoch, Appl. Geochem., 2001, 719-43 Seafood Household commodities Agriculture Antifoulings Industry Sediment Water Seafood Tap water pipes Food, beverage PVC-Materials - Agriculture - Antifoulings - Industry Used in - PVC-Materials TDI: 0.25 µg/kg bw/day ∑TBT, DBT, TPhT and DOT Legislation on OTCs in Food Contact Materials Compounds Maximum level                                      (µg Sn/kg foodstuff)     DBT, TBT, TPhT and DOT 40 (6)     MMT, DMT 180MOT 1200MDDT 12000 (50)DDDT 24000 (50)∑∑- Max levels on organotin migrating from the packaging material - Testing by the use of food simulators (water, acid, oil, alcohol etc) - BUT no maximum levels on organotins in the foodstuff itself!! Ref: EFSA (2005); proposed EFSA values in parenthesis FCM   → Foodstuff  migration →  Assumptions: - 1 kg food per 6 dm2 - 100 mL in contact with 0.6 dm2 GC coupled to ICPMS Heated Transferline GC ICPMS Picture from the lab at DTU Food …can be used to determine organotin compounds Organotin speciation by GC-ICPMS      • Chromatogram of 9 standards + IS      2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.000100020003000400050006000700080009000100001100012000130001400015000160001700018000190002000021000220002300024000Time-->AbundanceTIC: 026SMPL.D  0.34  0.59  2.01  3.13  4.00  5.25  6.42  7.16  7.51  8.11  8.36 10.58 11.21 11.78 12.64 12.90 13.48 14.88void DMT MMT Inorg Sn TBT DDDT MDDT DOT TPhT MOT DBT IS 15  10  5  min Derivatisation (ethylation) with NaBEt4 Organotin migration from Food Contact Materials      2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.0005001000150020002500300035004000450050005500600065007000750080008500Time-->AbundanceTIC: 014SMPL.D  4.07  5.77  6.46IS Inorg Sn DBT 6.306.326.346.366.386.406.426.446.466.486.506.526.546.566.586.6005001000150020002500300035004000Time-->AbundanceTIC: 005SMPL.DTIC: 014SMPL.DDBT   DBT concentration: 9.9 µg/kg      Overlaid standard and sample > EFSA guideline value of 6 µg/kg Output of DK survey: -33 samples -11 contained OT (mainly DBT) -3 exceeded EFSA guideline limit  Small scale survey on 33 Food Contact Materials Baking paper, PVC cling films, silicone baking forms, lids with PVC gaskets PUR-agglomerated cork wine stoppers •PVC lid •3% acetic acid Sloth&Trier et al, in prep Silver nanoparticles in products related to food and beverages http://www.nanotechproject.org/ Asymmetric flow field flow fractionation Inductively coupled plasma mass spectrometry (ICP-MS) Optical detection (multi angle and dynamic light scattering, UV and fluorescence) Particle separation according to their size (small NPs elute first) Particle detection (fractogram) Size determination Elemental detection for ID of the particles Quantification 01000000 50 90 130 170 210 250m/z90Zr140Ce138BaThe analytical platform AF4 – MALS - ICPMS Fraction collection for transmission electron microscopy (TEM) 100nm DTU Food, Technical University of Denmark 44nm 59nm Determination of Ag-nanoparticle size distribution   1 2 3 4 5 1 2 3 4 5 Loeschner et al, in prep  NanoLyse Project "Nanoparticles in Food: Analytical methods for detection and characterisation"  Validated methods for the  determination of inorganic ENP in food extracts, based on size separation, size determination and specific detection http://www.nanolyse.eu silica nanoparticles in tomato soup silver nanoparticles in lean meat Acknowledgements and funding sources     Coworkers: Rie R. Rasmussen, Rikke V. Hedegaard, Bjørn Schmidt, Xenia T. Trier, Katrin Löschner and Erik H. Larsen  Inge Rokkjær, Gudrun Hilbert and Dorthe L. Cederberg  Kåre Julshamn   Funding sources:  European Community's Seventh Framework Programme  Danish Food Administration (DFVA)  Norwegian Food Authority Thanks for your attention! 

ICPMS as an element-specific detector for the analysis of trace element species and nanoparticles

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ICPMS as an element-specific detector for the analysis of trace element species and nanoparticles

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