tof ms gc 8260...octocrylene (uv filter) pcb 179 may be responsible. in this study, we investigate...

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Monitoring water quality by passive sampling and GC×GCTOF MS with variable-energy electron ionisation Monitoring water quality by passive sampling and GC×GCTOF MS with variable-energy electron ionisation Monitoring water quality by passive sampling and GC×GCTOF MS with variable-energy electron ionisation Monitoring water quality by passive sampling and GC×GCTOF MS with variable-energy electron ionisation N. Watson 1 , L. McGregor 2 , S. Smith 2 , A. Gravell 3 , P. Kutty 3 , I. Allan 4 , and G.A. Mills 5 N. Watson 1 , L. McGregor 2 , S. Smith 2 , A. Gravell 3 , P. Kutty 3 , I. Allan 4 , and G.A. Mills 5 N. Watson , L. McGregor , S. Smith , A. Gravell , P. Kutty , I. Allan , and G.A. Mills 1 Markes International Inc., 11126-D Kenwood Road, Cincinnati, Ohio 45242, USA; 2 Markes International, Gwaun Elai Medi-Science Campus, Llantrisant, RCT, UK; 3 National Resources Wales (NRW), Llanelli, UK; 4 Norwegian Institute for Water Research (NIVA), 1 Markes International Inc., 11126-D Kenwood Road, Cincinnati, Ohio 45242, USA; 2 Markes International, Gwaun Elai Medi-Science Campus, Llantrisant, RCT, UK; 3 National Resources Wales (NRW), Llanelli, UK; 4 Norwegian Institute for Water Research (NIVA), Gaustadalleen 21, Oslo, Norway; 5 University of Portsmouth, School of Pharmacy and Biomedical Sciences, Portsmouth, UK. Gaustadalleen 21, Oslo, Norway; 5 University of Portsmouth, School of Pharmacy and Biomedical Sciences, Portsmouth, UK. Introduction Analysis of breast implants Experimental Persistent organic pollutants (POPs) Introduction Analysis of breast implants Experimental Persistent organic pollutants (POPs) A number of POPs were detected in the Two-dimensional gas chromatography with time-of-flight mass spectrometry (GC×GCTOF A BenchTOF-Select™ time-of-flight mass spectrometer In a second study, silicone breast prostheses obtained from patients over a wide age range A number of POPs were detected in the explanted breast prostheses, including numerous Two-dimensional gas chromatography with time-of-flight mass spectrometry (GC×GCTOF MS) can provide highly sensitive detection and confident mass spectral identification of A BenchTOF-Select™ time-of-flight mass spectrometer (Markes International) was used for all analyses, in In a second study, silicone breast prostheses obtained from patients over a wide age range were collected. Silicone oils in the prosthesis extracts were removed using the described explanted breast prostheses, including numerous PCBs (Figure 7), as well as several chlorinated Figure 7: MS) can provide highly sensitive detection and confident mass spectral identification of pollutants within complex environmental extracts. Nevertheless, the identification of (Markes International) was used for all analyses, in combination with a GC×GC gas chromatograph (Agilent were collected. Silicone oils in the prosthesis extracts were removed using the described multi-step extraction procedure, and the resultant extracts were analysed by GC×GCTOF MS PCBs (Figure 7), as well as several chlorinated pesticides, such as p,p-DDE. An ionization GC×GC surface pollutants within complex environmental extracts. Nevertheless, the identification of individual compounds may be hindered by weak molecular ions or when similar mass combination with a GC×GC gas chromatograph (Agilent 7890 GC with Zoex ZX1 modulator). multi-step extraction procedure, and the resultant extracts were analysed by GC×GCTOF MS with Select-eV. pesticides, such as p,p-DDE. An ionization energy of 14 eV enabled greater selectivity for plot showing a range of PCBs in an explanted breast individual compounds may be hindered by weak molecular ions or when similar mass spectral characteristics are evident across entire chemical classes. Select-eV ion source 7890 GC with Zoex ZX1 modulator). with Select-eV. energy of 14 eV enabled greater selectivity for such compounds by reducing spectral PCBs in an explanted breast prosthesis extract (summed EIC m/z spectral characteristics are evident across entire chemical classes. Select-eV ion source technology aims to combat this problem by allowing both hard and soft electron ionization Injection: PTV inlet splitless mode. Inlet temperature The analysed extracts were extremely complex (Figure 5), and contained a range of such compounds by reducing spectral fragmentation (Figure 8). prosthesis extract (summed EIC m/z [256 + 292 + 326 + 360 + 394 + 430]). technology aims to combat this problem by allowing both hard and soft electron ionization with no inherent loss in sensitivity. Injection: PTV inlet splitless mode. Inlet temperature 250°C (hold 1.2 min), 720°C/min to 300°C. compound types, including pharmaceuticals, hormones and persistent organic pollutants (POPs). fragmentation (Figure 8). [256 + 292 + 326 + 360 + 394 + 430]). with no inherent loss in sensitivity. 250°C (hold 1.2 min), 720°C/min to 300°C. The routine monitoring of water quality is now a requirement of environmental legislation, GC×GC: Column set: BPX5 (30 m × 250 µm × 0.25 µm) 70 eV 70 eV The routine monitoring of water quality is now a requirement of environmental legislation, such as the EU’s Water Framework Directive. Often the cause of poor water quality is and BPX50 (3 m × 100 µm × 0.10 µm). Oven: 65°C for PCBs Amgard TCMP (flame retardant) 70 eV p,p-DDE such as the EU’s Water Framework Directive. Often the cause of poor water quality is unknown, and extensive investigative monitoring is needed to determine what chemical 2.0 min, then 5°C/min to 315 °C (hold 5 min). No Figure 3: BenchTOF-Select Pharmaceuticals Octocrylene (UV filter) p,p-DDE PCB 179 unknown, and extensive investigative monitoring is needed to determine what chemical may be responsible. In this study, we investigate the parallel between passive sampling 2.0 min, then 5°C/min to 315 °C (hold 5 min). No secondary oven offset. Modulation time: 4 s. Hot-jet with GC×GC. Chloro-pesticides Tetrabromobenzene may be responsible. In this study, we investigate the parallel between passive sampling devices in river courses and silicon prostheses in the human body for the concentration of secondary oven offset. Modulation time: 4 s. Hot-jet pulse: 350 ms. devices in river courses and silicon prostheses in the human body for the concentration of environmental contaminants. This novel approach aims to better estimate the overall body pulse: 350 ms. BenchTOF-Select: 50 Hz; mass range: m/z 40500; ion source: 250°C; transfer line: 300°C. environmental contaminants. This novel approach aims to better estimate the overall body burden of bio-accumulative substances and how this changes over time of exposure. BenchTOF-Select: 50 Hz; mass range: m/z 40500; ion source: 250°C; transfer line: 300°C. burden of bio-accumulative substances and how this changes over time of exposure. This poster shows the suitability of this analytical platform for environmental investigations, Analysis of contaminated river water 14 eV 14 eV This poster shows the suitability of this analytical platform for environmental investigations, using both target-focused studies as well as non-targeted routines for screening for the Analysis of contaminated river water 14 eV using both target-focused studies as well as non-targeted routines for screening for the presence of emerging contaminants in two complex matrices. presence of emerging contaminants in two complex matrices. Initial studies focused on the analysis of environmental contaminants in a UK river using an Initial studies focused on the analysis of environmental contaminants in a UK river using an SPMD extract run at various ionization energies. It was discovered that, for the majority of Sample preparation SPMD extract run at various ionization energies. It was discovered that, for the majority of compounds, optimal sensitivity was achieved at 1214 eV. In the example shown in Figure Sample preparation compounds, optimal sensitivity was achieved at 1214 eV. In the example shown in Figure 4, the mass spectrum for galaxolide (a polycyclic musk commonly found in cosmetics) 4, the mass spectrum for galaxolide (a polycyclic musk commonly found in cosmetics) changes significantly with ionization energy. Figure 8: Mass spectra for two POPs, acquired at 70 eV and 14 eV using Select-eV. Passive sampling devices (e.g. semi-permeable membrane changes significantly with ionization energy. Figure 8: Mass spectra for two POPs, acquired at 70 eV and 14 eV using Select-eV. devices (SPMDs), LDPE and silicone rubber) are often used for Select-eV provides enhanced molecular ions whilst retaining structurally-significant The GC×GC plot of the control extract prepared using monitoring water quality. The samplers were deployed for Select-eV provides enhanced molecular ions whilst retaining structurally-significant fragment ions, delivering both confident compound identification and increased selectivity. The GC×GC plot of the control extract prepared using a new prosthesis was surprisingly complex (Figure 9), monitoring water quality. The samplers were deployed for several weeks in a polluted river course in the UK to effectively fragment ions, delivering both confident compound identification and increased selectivity. a new prosthesis was surprisingly complex (Figure 9), several weeks in a polluted river course in the UK to effectively sequester large volumes of water and provide a concentrated, containing aliphatic compounds and numerous PAHs sequester large volumes of water and provide a concentrated, representative extract for analysis by GC×GCTOF MS. Galaxolide Figure 5: GC×GCTOF MS contour plot of an explanted silicon breast prosthesis extract. (but none of the POPs or pharmaceuticals detected vs. representative extract for analysis by GC×GCTOF MS. Passive samplers enable minimal sample preparation, this 70 eV Figure 4: GC×GCTOF Galaxolide Figure 5: GC×GCTOF MS contour plot of an explanted silicon breast prosthesis extract. earlier). A possible explanation for this is that the vs. Passive samplers enable minimal sample preparation, this minimising the loss of possible compounds of interest. Full 70 eV MS contour plot of a earlier). A possible explanation for this is that the prosthesis is sampling chemicals from the air, minimising the loss of possible compounds of interest. Full experimental details for the collection and preparation of water river extract (left) and the transition in mass Pharmaceuticals prosthesis is sampling chemicals from the air, indicating that storage conditions should be rigorously experimental details for the collection and preparation of water samples have previously been reported. 1 the transition in mass spectral fragmentation Pharmaceuticals Lidocaine (a common painkiller) and Propofol (an analgesic) were detected in one of the indicating that storage conditions should be rigorously controlled in future studies. Figure 9: GC×GCTOF MS contour samples have previously been reported. 1 spectral fragmentation pattern with ionization Lidocaine (a common painkiller) and Propofol (an analgesic) were detected in one of the controlled in future studies. Figure 9: GC×GCTOF MS contour plot of a new prosthesis extract. Three removed implant samples (as well as a new prosthesis pattern with ionization energy (right). prosthesis extracts. Select-eV ionization (14 eV) improved the absolute abundance of the plot of a new prosthesis extract. Conclusions Three removed implant samples (as well as a new prosthesis as the control blank) were extracted through MeOHwater 14 eV energy (right). molecular ion in both cases, leading to improved limits of detection (Figure 6). Conclusions as the control blank) were extracted through MeOHwater (80:20 v/v; 300400 mL) into cyclohexane in 2 L beakers 14 eV (80:20 v/v; 300400 mL) into cyclohexane in 2 L beakers (Figure 2). Extraction using 200300 mL cyclohexane was Propofol Figure 1: Semi-permeable (Figure 2). Extraction using 200300 mL cyclohexane was repeated twice over the course of a week. The cyclohexane Lidocaine 70 eV Propofol 70 eV We have shown in this poster that GC×GCTOF MS is an ideal choice for the analysis of Figure 1: Semi-permeable membrane device (SPMD, repeated twice over the course of a week. The cyclohexane phases were then combined and 70 eV M +· = 26,177 70 eV We have shown in this poster that GC×GCTOF MS is an ideal choice for the analysis of complex extracts from breast implants, and that Select-eV greatly improves screening membrane device (SPMD, top) and explanted silicon phases were then combined and reduced to 2 mL and spiked with M +· = 26,177 counts complex extracts from breast implants, and that Select-eV greatly improves screening capabilities, by simplifying targeted spectra and increasing both sensitivity and selectivity. breast prosthesis (bottom). reduced to 2 mL and spiked with counts capabilities, by simplifying targeted spectra and increasing both sensitivity and selectivity. an internal standard mix (100 ng 12 eV In addition, we have identified this approach as a step towards achieving better understanding of CB-30, CB-53 and CB-204). 12 eV of the overall body burden of bio-accumulative substances, and how this changes with time. Cyclohexane For this study, a 0.5 mL aliquot was exchanged to methanol 14 eV Future studies will focus on quantitative extraction of targets from the implant samples, MeOHwater Cyclohexane For this study, a 0.5 mL aliquot was exchanged to methanol and diluted with water. Compounds were then picked-up 14 eV 14 eV Future studies will focus on quantitative extraction of targets from the implant samples, to better gauge their health impacts and allow levels in the body and environmental MeOHwater and diluted with water. Compounds were then picked-up with clean silicone rubber (AlteSil, 24 g). The silicone M +· = 71,206 counts to better gauge their health impacts and allow levels in the body and environmental matrices (e.g. drinking water) to be compared. Prosthesis with clean silicone rubber (AlteSil, 24 g). The silicone counts matrices (e.g. drinking water) to be compared. rubber was then extracted with cyclohexane and reduced. 10 eV Acknowledgement Figure 2: Extraction of 1 A. Gravell et al., GC×GCTOF MS complements passive sampling Acknowledgement compounds of interest from a 1 A. Gravell et al., GC×GCTOF MS complements passive sampling for the screening of pollutants in water, LCGC: Current Trends in Figure 6: Mass spectra for two pharmaceuticals, acquired at 70 eV and 14 eV using Select-eV. The authors kindly acknowledge the work of plastic surgeon Helge E. Roald (Colosseum silicon breast prosthesis. for the screening of pollutants in water, LCGC: Current Trends in Mass Spectrometry, March 2013, pp. 814. Figure 6: Mass spectra for two pharmaceuticals, acquired at 70 eV and 14 eV using Select-eV. The authors kindly acknowledge the work of plastic surgeon Helge E. Roald (Colosseum Clinic, Oslo, Norway) for providing the prostheses used in this study. Mass Spectrometry, March 2013, pp. 814. Clinic, Oslo, Norway) for providing the prostheses used in this study. Markes International Markes International Markes International T: 866-483-5684 (toll-free) F: 513-745-0741 E: [email protected] W: www.markes.com T: 866-483-5684 (toll-free) F: 513-745-0741 E: [email protected] W: www.markes.com T: 866-483-5684 (toll-free) F: 513-745-0741 E: [email protected] W: www.markes.com

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    ectra

    l cha

    ract

    eris

    tics

    are

    evid

    ent a

    cros

    s en

    tire

    chem

    ical

    cla

    sses

    . Sel

    ect-e

    V io

    n so

    urce

    te

    chno

    logy

    aim

    s to

    com

    bat t

    his

    prob

    lem

    by

    allo

    win

    g bo

    th h

    ard

    and

    soft

    elec

    tron

    ioni

    zatio

    n In

    ject

    ion:

    PTV

    inle

    t spl

    itles

    s m

    ode.

    Inle

    t tem

    pera

    ture

    Th

    e an

    alys

    ed e

    xtra

    cts

    wer

    e ex

    trem

    ely

    com

    plex

    (Fig

    ure

    5), a

    nd c

    onta

    ined

    a ra

    nge

    of

    such

    com

    poun

    ds b

    y re

    duci

    ng s

    pect

    ral

    fragm

    enta

    tion

    (Fig

    ure

    8).

    pros

    thes

    is e

    xtra

    ct (s

    umm

    ed E

    IC m

    /z

    [256

    + 2

    92 +

    326

    + 3

    60 +

    394

    + 4

    30]).

    te

    chno

    logy

    aim

    s to

    com

    bat t

    his

    prob

    lem

    by

    allo

    win

    g bo

    th h

    ard

    and

    soft

    elec

    tron

    ioni

    zatio

    n w

    ith n

    o in

    here

    nt lo

    ss in

    sen

    sitiv

    ity.

    Inje

    ctio

    n: P

    TV in

    let s

    plitl

    ess

    mod

    e. In

    let t

    empe

    ratu

    re

    250°

    C (h

    old

    1.2

    min

    ), 72

    0°C

    /min

    to 3

    00°C

    .Th

    e an

    alys

    ed e

    xtra

    cts

    wer

    e ex

    trem

    ely

    com

    plex

    (Fig

    ure

    5), a

    nd c

    onta

    ined

    a ra

    nge

    of

    com

    poun

    d ty

    pes,

    incl

    udin

    g ph

    arm

    aceu

    tical

    s, h

    orm

    ones

    and

    per

    sist

    ent o

    rgan

    ic p

    ollu

    tant

    s (P

    OPs

    ).fra

    gmen

    tatio

    n (F

    igur

    e 8)

    . [2

    56 +

    292

    + 3

    26 +

    360

    + 3

    94 +

    430

    ]).

    with

    no

    inhe

    rent

    loss

    in s

    ensi

    tivity

    .25

    0°C

    (hol

    d 1.

    2 m

    in),

    720°

    C/m

    in to

    300

    °C.

    com

    poun

    d ty

    pes,

    incl

    udin

    g ph

    arm

    aceu

    tical

    s, h

    orm

    ones

    and

    per

    sist

    ent o

    rgan

    ic p

    ollu

    tant

    s (P

    OPs

    ).

    The

    rout

    ine

    mon

    itorin

    g of

    wat

    er q

    ualit

    y is

    now

    a re

    quire

    men

    t of e

    nviro

    nmen

    tal l

    egis

    latio

    n,

    GC

    ×GC

    :Col

    umn

    set:

    BP

    X5

    (30

    m ×

    250

    µm ×

    0.25

    µm

    ) 70

    eV

    70 e

    VTh

    e ro

    utin

    e m

    onito

    ring

    of w

    ater

    qua

    lity

    is n

    ow a

    requ

    irem

    ent o

    f env

    ironm

    enta

    l leg

    isla

    tion,

    su

    ch a

    s th

    e E

    U’s

    Wat

    er F

    ram

    ewor

    k D

    irect

    ive.

    Ofte

    n th

    e ca

    use

    of p

    oor w

    ater

    qua

    lity

    is

    GC

    ×GC

    :Col

    umn

    set:

    BP

    X5

    (30

    m ×

    250

    µm ×

    0.25

    µm

    ) an

    d B

    PX

    50 (3

    m ×

    100

    µm ×

    0.10

    µm

    ). O

    ven:

    65°

    C fo

    r P

    CB

    sA

    mga

    rd T

    CM

    P (fl

    ame

    reta

    rdan

    t)70

    eV

    70 e

    Vp,

    p′-D

    DE

    such

    as

    the

    EU

    ’s W

    ater

    Fra

    mew

    ork

    Dire

    ctiv

    e. O

    ften

    the

    caus

    e of

    poo

    r wat

    er q

    ualit

    y is

    un

    know

    n, a

    nd e

    xten

    sive

    inve

    stig

    ativ

    e m

    onito

    ring

    is n

    eede

    d to

    det

    erm

    ine

    wha

    t che

    mic

    al

    and

    BP

    X50

    (3 m

    ×10

    0 µm

    ×0.

    10 µ

    m).

    Ove

    n: 6

    5°C

    for

    2.0

    min

    , the

    n 5°

    C/m

    in to

    315

    °C

    (hol

    d 5

    min

    ). N

    o Fi

    gure

    3:B

    ench

    TOF-

    Sel

    ect

    PC

    Bs

    Pha

    rmac

    eutic

    als

    Am

    gard

    TC

    MP

    (flam

    e re

    tard

    ant)

    Oct

    ocry

    lene

    (UV

    filte

    r)p,

    p′-D

    DE

    PC

    B 1

    79un

    know

    n, a

    nd e

    xten

    sive

    inve

    stig

    ativ

    e m

    onito

    ring

    is n

    eede

    d to

    det

    erm

    ine

    wha

    t che

    mic

    al

    may

    be

    resp

    onsi

    ble.

    In th

    is s

    tudy

    , we

    inve

    stig

    ate

    the

    para

    llel b

    etw

    een

    pass

    ive

    sam

    plin

    g

    2.0

    min

    , the

    n 5°

    C/m

    in to

    315

    °C

    (hol

    d 5

    min

    ). N

    o se

    cond

    ary

    oven

    offs

    et. M

    odul

    atio

    n tim

    e: 4

    s. H

    ot-je

    t Fi

    gure

    3:B

    ench

    TOF-

    Sel

    ect

    with

    GC

    ×GC

    .P

    harm

    aceu

    tical

    s C

    hlor

    o-pe

    stic

    ides

    Oct

    ocry

    lene

    (UV

    filte

    r)Te

    trabr

    omob

    enze

    nem

    ay b

    e re

    spon

    sibl

    e. In

    this

    stu

    dy, w

    e in

    vest

    igat

    e th

    e pa

    ralle

    l bet

    wee

    n pa

    ssiv

    e sa

    mpl

    ing

    devi

    ces

    in ri

    ver c

    ours

    es a

    nd s

    ilico

    n pr

    osth

    eses

    in th

    e hu

    man

    bod

    y fo

    r the

    con

    cent

    ratio

    n of

    seco

    ndar

    y ov

    en o

    ffset

    . Mod

    ulat

    ion

    time:

    4 s

    . Hot

    -jet

    puls

    e: 3

    50 m

    s.C

    hlor

    o-pe

    stic

    ides

    Tetra

    brom

    oben

    zene

    devi

    ces

    in ri

    ver c

    ours

    es a

    nd s

    ilico

    n pr

    osth

    eses

    in th

    e hu

    man

    bod

    y fo

    r the

    con

    cent

    ratio

    n of

    en

    viro

    nmen

    tal c

    onta

    min

    ants

    . Thi

    s no

    vel a

    ppro

    ach

    aim

    s to

    bet

    ter e

    stim

    ate

    the

    over

    all b

    ody

    puls

    e: 3

    50 m

    s.B

    ench

    TOF-

    Sele

    ct: 5

    0 H

    z; m

    ass

    rang

    e: m

    /z 4

    0–50

    0; io

    n so

    urce

    : 250

    °C; t

    rans

    fer l

    ine:

    300

    °C.

    envi

    ronm

    enta

    l con

    tam

    inan

    ts. T

    his

    nove

    l app

    roac

    h ai

    ms

    to b

    ette

    r est

    imat

    e th

    e ov

    eral

    l bod

    y bu

    rden

    of b

    io-a

    ccum

    ulat

    ive

    subs

    tanc

    es a

    nd h

    ow th

    is c

    hang

    es o

    ver t

    ime

    of e

    xpos

    ure.

    Ben

    chTO

    F-Se

    lect

    : 50

    Hz;

    mas

    s ra

    nge:

    m/z

    40–

    500;

    ion

    sour

    ce: 2

    50°C

    ; tra

    nsfe

    r lin

    e: 3

    00°C

    .bu

    rden

    of b

    io-a

    ccum

    ulat

    ive

    subs

    tanc

    es a

    nd h

    ow th

    is c

    hang

    es o

    ver t

    ime

    of e

    xpos

    ure.

    This

    pos

    ter s

    how

    s th

    e su

    itabi

    lity

    of th

    is a

    naly

    tical

    pla

    tform

    for e

    nviro

    nmen

    tal i

    nves

    tigat

    ions

    , A

    naly

    sis

    of c

    onta

    min

    ated

    rive

    r wat

    er14

    eV

    14 e

    VTh

    is p

    oste

    r sho

    ws

    the

    suita

    bilit

    y of

    this

    ana

    lytic

    al p

    latfo

    rm fo

    r env

    ironm

    enta

    l inv

    estig

    atio

    ns,

    usin

    g bo

    th ta

    rget

    -focu

    sed

    stud

    ies

    as w

    ell a

    s no

    n-ta

    rget

    ed ro

    utin

    es fo

    r scr

    eeni

    ng fo

    r the

    A

    naly

    sis

    of c

    onta

    min

    ated

    rive

    r wat

    er14

    eV

    usin

    g bo

    th ta

    rget

    -focu

    sed

    stud

    ies

    as w

    ell a

    s no

    n-ta

    rget

    ed ro

    utin

    es fo

    r scr

    eeni

    ng fo

    r the

    pr

    esen

    ce o

    f em

    ergi

    ng c

    onta

    min

    ants

    in tw

    o co

    mpl

    ex m

    atric

    es.

    pres

    ence

    of e

    mer

    ging

    con

    tam

    inan

    ts in

    two

    com

    plex

    mat

    rices

    .In

    itial

    stu

    dies

    focu

    sed

    on th

    e an

    alys

    is o

    f env

    ironm

    enta

    l con

    tam

    inan

    ts in

    a U

    K ri

    ver u

    sing

    an

    Initi

    al s

    tudi

    es fo

    cuse

    d on

    the

    anal

    ysis

    of e

    nviro

    nmen

    tal c

    onta

    min

    ants

    in a

    UK

    rive

    r usi

    ng a

    n S

    PM

    D e

    xtra

    ct ru

    n at

    var

    ious

    ioni

    zatio

    n en

    ergi

    es. I

    t was

    dis

    cove

    red

    that

    , for

    the

    maj

    ority

    of

    Sam

    ple

    prep

    arat

    ion

    SP

    MD

    ext

    ract

    run

    at v

    ario

    us io

    niza

    tion

    ener

    gies

    . It w

    as d

    isco

    vere

    d th

    at, f

    or th

    e m

    ajor

    ity o

    f co

    mpo

    unds

    , opt

    imal

    sen

    sitiv

    ity w

    as a

    chie

    ved

    at 1

    2–14

    eV.

    In th

    e ex

    ampl

    e sh

    own

    in F

    igur

    e Sa

    mpl

    e pr

    epar

    atio

    nco

    mpo

    unds

    , opt

    imal

    sen

    sitiv

    ity w

    as a

    chie

    ved

    at 1

    2–14

    eV.

    In th

    e ex

    ampl

    e sh

    own

    in F

    igur

    e 4,

    the

    mas

    s sp

    ectru

    m fo

    r gal

    axol

    ide

    (a p

    olyc

    yclic

    mus

    k co

    mm

    only

    foun

    d in

    cos

    met

    ics)

    4,

    the

    mas

    s sp

    ectru

    m fo

    r gal

    axol

    ide

    (a p

    olyc

    yclic

    mus

    k co

    mm

    only

    foun

    d in

    cos

    met

    ics)

    ch

    ange

    s si

    gnifi

    cant

    ly w

    ith io

    niza

    tion

    ener

    gy.

    Figu

    re 8

    :Mas

    s sp

    ectra

    for t

    wo

    PO

    Ps,

    acq

    uire

    d at

    70

    eV a

    nd 1

    4 eV

    usi

    ng S

    elec

    t-eV.

    Pas

    sive

    sam

    plin

    g de

    vice

    s (e

    .g.s

    emi-p

    erm

    eabl

    e m

    embr

    ane

    chan

    ges

    sign

    ifica

    ntly

    with

    ioni

    zatio

    n en

    ergy

    . Fi

    gure

    8:M

    ass

    spec

    tra fo

    r tw

    o P

    OP

    s, a

    cqui

    red

    at 7

    0 eV

    and

    14

    eV u

    sing

    Sel

    ect-e

    V.P

    assi

    ve s

    ampl

    ing

    devi

    ces

    (e.g

    .sem

    i-per

    mea

    ble

    mem

    bran

    e de

    vice

    s (S

    PM

    Ds)

    , LD

    PE

    and

    sili

    cone

    rubb

    er) a

    re o

    ften

    used

    for

    Sel

    ect-e

    V p

    rovi

    des

    enha

    nced

    mol

    ecul

    ar io

    ns w

    hils

    t ret

    aini

    ng s

    truct

    ural

    ly-s

    igni

    fican

    t Th

    e G

    C×G

    C p

    lot o

    f the

    con

    trol e

    xtra

    ct p

    repa

    red

    usin

    g de

    vice

    s (S

    PM

    Ds)

    , LD

    PE

    and

    sili

    cone

    rubb

    er) a

    re o

    ften

    used

    for

    mon

    itorin

    g w

    ater

    qua

    lity.

    The

    sam

    pler

    s w

    ere

    depl

    oyed

    for

    Sel

    ect-e

    V p

    rovi

    des

    enha

    nced

    mol

    ecul

    ar io

    ns w

    hils

    t ret

    aini

    ng s

    truct

    ural

    ly-s

    igni

    fican

    t fra

    gmen

    t ion

    s, d

    eliv

    erin

    g bo

    th c

    onfid

    ent c

    ompo

    und

    iden

    tific

    atio

    n an

    d in

    crea

    sed

    sele

    ctiv

    ity.

    The

    GC

    ×GC

    plo

    t of t

    he c

    ontro

    l ext

    ract

    pre

    pare

    d us

    ing

    a ne

    w p

    rost

    hesi

    s w

    as s

    urpr

    isin

    gly

    com

    plex

    (Fig

    ure

    9),

    mon

    itorin

    g w

    ater

    qua

    lity.

    The

    sam

    pler

    s w

    ere

    depl

    oyed

    for

    seve

    ral w

    eeks

    in a

    pol

    lute

    d riv

    er c

    ours

    e in

    the

    UK

    to e

    ffect

    ivel

    y fra

    gmen

    t ion

    s, d

    eliv

    erin

    g bo

    th c

    onfid

    ent c

    ompo

    und

    iden

    tific

    atio

    n an

    d in

    crea

    sed

    sele

    ctiv

    ity.

    a ne

    w p

    rost

    hesi

    s w

    as s

    urpr

    isin

    gly

    com

    plex

    (Fig

    ure

    9),

    seve

    ral w

    eeks

    in a

    pol

    lute

    d riv

    er c

    ours

    e in

    the

    UK

    to e

    ffect

    ivel

    y se

    ques

    ter l

    arge

    vol

    umes

    of w

    ater

    and

    pro

    vide

    a c

    once

    ntra

    ted,

    co

    ntai

    ning

    alip

    hatic

    com

    poun

    dsan

    d nu

    mer

    ous

    PAH

    s se

    ques

    ter l

    arge

    vol

    umes

    of w

    ater

    and

    pro

    vide

    a c

    once

    ntra

    ted,

    re

    pres

    enta

    tive

    extra

    ct fo

    r ana

    lysi

    s by

    GC

    ×GC

    –TO

    F M

    S.

    Gal

    axol

    ide

    Figu

    re 5

    :GC

    ×GC

    –TO

    F M

    S c

    onto

    ur p

    lot o

    f an

    expl

    ante

    d si

    licon

    bre

    ast p

    rost

    hesi

    s ex

    tract

    .co

    ntai

    ning

    alip

    hatic

    com

    poun

    dsan

    d nu

    mer

    ous

    PAH

    s (b

    ut n

    one

    of th

    e P

    OP

    s or

    pha

    rmac

    eutic

    als

    dete

    cted

    vs

    .re

    pres

    enta

    tive

    extra

    ct fo

    r ana

    lysi

    s by

    GC

    ×GC

    –TO

    F M

    S.

    Pas

    sive

    sam

    pler

    s en

    able

    min

    imal

    sam

    ple

    prep

    arat

    ion,

    this

    70

    eV

    Figu

    re 4

    :GC

    ×GC

    –TO

    F G

    alax

    olid

    eFi

    gure

    5:G

    C×G

    C–T

    OF

    MS

    con

    tour

    plo

    t of a

    n ex

    plan

    ted

    silic

    on b

    reas

    t pro

    sthe

    sis

    extra

    ct.

    (but

    non

    e of

    the

    PO

    Ps

    or p

    harm

    aceu

    tical

    s de

    tect

    ed

    earli

    er).

    A po

    ssib

    le e

    xpla

    natio

    n fo

    r thi

    s is

    that

    the

    vs.

    Pas

    sive

    sam

    pler

    s en

    able

    min

    imal

    sam

    ple

    prep

    arat

    ion,

    this

    m

    inim

    isin

    g th

    e lo

    ss o

    f pos

    sibl

    e co

    mpo

    unds

    of i

    nter

    est.

    Full

    70 e

    VFi

    gure

    4:G

    C×G

    C–T

    OF

    MS

    con

    tour

    plo

    t of a

    ea

    rlier

    ). A

    poss

    ible

    exp

    lana

    tion

    for t

    his

    is th

    at th

    e pr

    osth

    esis

    is s

    ampl

    ing

    chem

    ical

    s fro

    m th

    e ai

    r, m

    inim

    isin

    g th

    e lo

    ss o

    f pos

    sibl

    e co

    mpo

    unds

    of i

    nter

    est.

    Full

    expe

    rimen

    tal d

    etai

    ls fo

    r the

    col

    lect

    ion

    and

    prep

    arat

    ion

    of w

    ater

    riv

    er e

    xtra

    ct (l

    eft)

    and

    the

    trans

    ition

    in m

    ass

    Phar

    mac

    eutic

    als

    pros

    thes

    is is

    sam

    plin

    g ch

    emic

    als

    from

    the

    air,

    indi

    catin

    g th

    at s

    tora

    ge c

    ondi

    tions

    sho

    uld

    be ri

    goro

    usly

    expe

    rimen

    tal d

    etai

    ls fo

    r the

    col

    lect

    ion

    and

    prep

    arat

    ion

    of w

    ater

    sa

    mpl

    es h

    ave

    prev

    ious

    ly b

    een

    repo

    rted.

    1th

    e tra

    nsiti

    on in

    mas

    s sp

    ectra

    l fra

    gmen

    tatio

    n

    Phar

    mac

    eutic

    als

    Lido

    cain

    e (a

    com

    mon

    pai

    nkill

    er) a

    nd P

    ropo

    fol(

    an a

    nalg

    esic

    ) wer

    e de

    tect

    ed in

    one

    of t

    he

    indi

    catin

    g th

    at s

    tora

    ge c

    ondi

    tions

    sho

    uld

    be ri

    goro

    usly

    cont

    rolle

    d in

    futu

    re s

    tudi

    es.

    Figu

    re 9

    :GC

    ×GC

    –TO

    F M

    S c

    onto

    ur

    sam

    ples

    hav

    e pr

    evio

    usly

    bee

    n re

    porte

    d.1

    spec

    tral f

    ragm

    enta

    tion

    patte

    rn w

    ith io

    niza

    tion

    Lido

    cain

    e (a

    com

    mon

    pai

    nkill

    er) a

    nd P

    ropo

    fol(

    an a

    nalg

    esic

    ) wer

    e de

    tect

    ed in

    one

    of t

    he

    cont

    rolle

    d in

    futu

    re s

    tudi

    es.

    Figu

    re 9

    :GC

    ×GC

    –TO

    F M

    S c

    onto

    ur

    plot

    of a

    new

    pro

    sthe

    sis

    extra

    ct.

    Thre

    e re

    mov

    ed im

    plan

    t sam

    ples

    (as

    wel

    l as

    a ne

    w p

    rost

    hesi

    spa

    ttern

    with

    ioni

    zatio

    n en

    ergy

    (rig

    ht).

    pros

    thes

    is e

    xtra

    cts.

    Sel

    ect-e

    Vio

    niza

    tion

    (14

    eV) i

    mpr

    oved

    the

    abso

    lute

    abu

    ndan

    ce o

    f the

    pl

    ot o

    f a n

    ew p

    rost

    hesi

    s ex

    tract

    .

    Con

    clus

    ions

    Thre

    e re

    mov

    ed im

    plan

    t sam

    ples

    (as

    wel

    l as

    a ne

    w p

    rost

    hesi

    sas

    the

    cont

    rol b

    lank

    ) wer

    e ex

    tract

    ed th

    roug

    h M

    eOH

    –wat

    er

    14 e

    V

    ener

    gy (r

    ight

    ). pr

    osth

    esis

    ext

    ract

    s. S

    elec

    t-eV

    ioni

    zatio

    n (1

    4 eV

    ) im

    prov

    ed th

    e ab

    solu

    te a

    bund

    ance

    of t

    he

    mol

    ecul

    ar io

    n in

    bot

    h ca

    ses,

    lead

    ing

    to im

    prov

    ed li

    mits

    of d

    etec

    tion

    (Fig

    ure

    6).

    Con

    clus

    ions

    as th

    e co

    ntro

    l bla

    nk) w

    ere

    extra

    cted

    thro

    ugh

    MeO

    H–w

    ater

    (8

    0:20

    v/v

    ;300

    –400

    mL)

    into

    cyc

    lohe

    xane

    in 2

    L b

    eake

    rs

    14 e

    Vm

    olec

    ular

    ion

    in b

    oth

    case

    s, le

    adin

    g to

    impr

    oved

    lim

    its o

    f det

    ectio

    n (F

    igur

    e 6)

    . C

    oncl

    usio

    ns(8

    0:20

    v/v

    ;300

    –400

    mL)

    into

    cyc

    lohe

    xane

    in 2

    L b

    eake

    rs

    (Fig

    ure

    2). E

    xtra

    ctio

    n us

    ing

    200–

    300

    mL

    cycl

    ohex

    ane

    was

    P

    ropo

    fol

    Figu

    re 1

    :Sem

    i-per

    mea

    ble

    (Fig

    ure

    2). E

    xtra

    ctio

    n us

    ing

    200–

    300

    mL

    cycl

    ohex

    ane

    was

    re

    peat

    ed tw

    ice

    over

    the

    cour

    se o

    f a w

    eek.

    The

    cyc

    lohe

    xane

    Li

    doca

    ine

    70 e

    VP

    ropo

    fol

    70 e

    VW

    e ha

    ve s

    how

    n in

    this

    pos

    ter t

    hat G

    C×G

    C–T

    OF

    MS

    is a

    n id

    eal c

    hoic

    e fo

    r the

    ana

    lysi

    s of

    Fi

    gure

    1:S

    emi-p

    erm

    eabl

    e m

    embr

    ane

    devi

    ce (S

    PM

    D,

    repe

    ated

    twic

    e ov

    er th

    e co

    urse

    of a

    wee

    k. T

    he c

    yclo

    hexa

    ne

    phas

    es w

    ere

    then

    com

    bine

    d an

    d

    Lido

    cain

    e70

    eV

    M+·

    = 26

    ,177

    70 e

    VW

    e ha

    ve s

    how

    n in

    this

    pos

    ter t

    hat G

    C×G

    C–T

    OF

    MS

    is a

    n id

    eal c

    hoic

    e fo

    r the

    ana

    lysi

    s of

    co

    mpl

    ex e

    xtra

    cts

    from

    bre

    ast i

    mpl

    ants

    , and

    that

    Sel

    ect-e

    V g

    reat

    ly im

    prov

    es s

    cree

    ning

    m

    embr

    ane

    devi

    ce (S

    PM

    D,

    top)

    and

    exp

    lant

    ed s

    ilico

    n ph

    ases

    wer

    e th

    en c

    ombi

    ned

    and

    redu

    ced

    to 2

    mL

    and

    spik

    ed w

    ithM

    +·=

    26,1

    77co

    unts

    co

    mpl

    ex e

    xtra

    cts

    from

    bre

    ast i

    mpl

    ants

    , and

    that

    Sel

    ect-e

    V g

    reat

    ly im

    prov

    es s

    cree

    ning

    ca

    pabi

    litie

    s, b

    y si

    mpl

    ifyin

    g ta

    rget

    ed s

    pect

    ra a

    nd in

    crea

    sing

    bot

    h se

    nsiti

    vity

    and

    sel

    ectiv

    ity.

    top)

    and

    exp

    lant

    ed s

    ilico

    n br

    east

    pro

    sthe

    sis

    (bot

    tom

    ).re

    duce

    d to

    2 m

    Lan

    d sp

    iked

    with

    coun

    ts

    capa

    bilit

    ies,

    by

    sim

    plify

    ing

    targ

    eted

    spe

    ctra

    and

    incr

    easi

    ng b

    oth

    sens

    itivi

    ty a

    nd s

    elec

    tivity

    .an

    inte

    rnal

    sta

    ndar

    d m

    ix (1

    00 n

    g12

    eV

    In a

    dditi

    on, w

    e ha

    ve id

    entif

    ied

    this

    app

    roac

    h as

    a s

    tep

    tow

    ards

    ach

    ievi

    ng b

    ette

    r und

    erst

    andi

    ngan

    inte

    rnal

    sta

    ndar

    d m

    ix (1

    00 n

    gof

    CB

    -30,

    CB

    -53

    and

    CB

    -204

    ).12

    eV

    In a

    dditi

    on, w

    e ha

    ve id

    entif

    ied

    this

    app

    roac

    h as

    a s

    tep

    tow

    ards

    ach

    ievi

    ng b

    ette

    r und

    erst

    andi

    ngof

    the

    over

    all b

    ody

    burd

    en o

    f bio

    -acc

    umul

    ativ

    e su

    bsta

    nces

    , and

    how

    this

    cha

    nges

    with

    tim

    e.of

    CB

    -30,

    CB

    -53

    and

    CB

    -204

    ).C

    yclo

    hexa

    neFo

    r thi

    s st

    udy,

    a 0

    .5 m

    L al

    iquo

    t was

    exc

    hang

    ed to

    met

    hano

    l 14

    eV

    of th

    e ov

    eral

    l bod

    y bu

    rden

    of b

    io-a

    ccum

    ulat

    ive

    subs

    tanc

    es, a

    nd h

    ow th

    is c

    hang

    es w

    ith ti

    me.

    Futu

    re s

    tudi

    es w

    ill fo

    cus

    on q

    uant

    itativ

    e ex

    tract

    ion

    of ta

    rget

    s fro

    m th

    e im

    plan

    t sam

    ples

    , M

    eOH

    –wat

    erC

    yclo

    hexa

    neFo

    r thi

    s st

    udy,

    a 0

    .5 m

    L al

    iquo

    t was

    exc

    hang

    ed to

    met

    hano

    l an

    d di

    lute

    d w

    ith w

    ater

    . Com

    poun

    ds w

    ere

    then

    pic

    ked-

    up

    14 e

    V14

    eV

    Futu

    re s

    tudi

    es w

    ill fo

    cus

    on q

    uant

    itativ

    e ex

    tract

    ion

    of ta

    rget

    s fro

    m th

    e im

    plan

    t sam

    ples

    , to

    bet

    ter g

    auge

    thei

    r hea

    lth im

    pact

    s an

    d al

    low

    leve

    ls in

    the

    body

    and

    env

    ironm

    enta

    l M

    eOH

    –wat

    eran

    d di

    lute

    d w

    ith w

    ater

    . Com

    poun

    ds w

    ere

    then

    pic

    ked-

    up

    with

    cle

    an s

    ilico

    ne ru

    bber

    (Alte

    Sil,

    2–4

    g).

    The

    silic

    one

    M+·

    = 71

    ,206

    coun

    ts

    14 e

    Vto

    bet

    ter g

    auge

    thei

    r hea

    lth im

    pact

    s an

    d al

    low

    leve

    ls in

    the

    body

    and

    env

    ironm

    enta

    l m

    atric

    es (e

    .g.d

    rinki

    ng w

    ater

    ) to

    be c

    ompa

    red.

    Pro

    sthe

    sis

    with

    cle

    an s

    ilico

    ne ru

    bber

    (Alte

    Sil,

    2–4

    g).

    The

    silic

    one

    coun

    ts

    mat

    rices

    (e.g

    .drin

    king

    wat

    er) t

    o be

    com

    pare

    d.P

    rost

    hesi

    sw

    ith c

    lean

    sili

    cone

    rubb

    er (A

    lteS

    il, 2

    –4 g

    ). Th

    e si

    licon

    e ru

    bber

    was

    then

    ext

    ract

    ed w

    ith c

    yclo

    hexa

    ne a

    nd re

    duce

    d.10

    eV

    rubb

    er w

    as th

    en e

    xtra

    cted

    with

    cyc

    lohe

    xane

    and

    redu

    ced.

    Ack

    now

    ledg

    emen

    tFi

    gure

    2:E

    xtra

    ctio

    n of

    1

    A. G

    rave

    ll et

    al.,

    GC

    ×GC

    –TO

    F M

    S c

    ompl

    emen

    ts p

    assi

    ve s

    ampl

    ing

    Ack

    now

    ledg

    emen

    tFi

    gure

    2:E

    xtra

    ctio

    n of

    co

    mpo

    unds

    of i

    nter

    est f

    rom

    a

    1A

    . Gra

    vell

    et a

    l., G

    C×G

    C–T

    OF

    MS

    com

    plem

    ents

    pas

    sive

    sam

    plin

    g fo

    r the

    scr

    eeni

    ng o

    f pol

    luta

    nts

    in w

    ater

    , LC

    GC

    : Cur

    rent

    Tre

    nds

    in

    Figu

    re 6

    :Mas

    s sp

    ectra

    for t

    wo

    phar

    mac

    eutic

    als,

    acq

    uire

    d at

    70

    eV a

    nd 1

    4 eV

    usi

    ng S

    elec

    t-eV.

    The

    auth

    ors

    kind

    ly a

    ckno

    wle

    dge

    the

    wor

    k of

    pla

    stic

    sur

    geon

    Hel

    ge E

    . Roa

    ld (C

    olos

    seum

    silic

    on b

    reas

    t pro

    sthe

    sis.

    for t

    he s

    cree

    ning

    of p

    ollu

    tant

    s in

    wat

    er, L

    CG

    C: C

    urre

    nt T

    rend

    s in

    M

    ass

    Spe

    ctro

    met

    ry, M

    arch

    201

    3, p

    p. 8

    –14.

    Figu

    re 6

    :Mas

    s sp

    ectra

    for t

    wo

    phar

    mac

    eutic

    als,

    acq

    uire

    d at

    70

    eV a

    nd 1

    4 eV

    usi

    ng S

    elec

    t-eV.

    The

    auth

    ors

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    wor

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    ) for

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    e pr

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    d in

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    stu

    dy.

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    ch 2

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    pp.

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    o, N

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