Aristide P. Ganci1, Tabiwang N. Arrey2, Thomas Moehring2, and Stuart Harrad1
University of Birmingham, School of Geography, Earth and Environmental Sciences, Birmingham, United Kingdom
2
Thermo Fisher Scientific, Bremen, Germany
Poster Note 6475 9
Method Development for the Identification of
Novel Brominated Flame Retardants Using a
Q Exactive HRAM Hass Spectrometer
Method
Method development
development for
for the
the identification
identification of
of nove
nove
1
1Universityof
Aristide
AristideP.P.Ganci
Ganci1,1,Tabiwang
TabiwangN.
N.Arrey
Arrey2,2,Thomas
ThomasMoehring
Moehring2 2and
andStuart
StuartHarrad
Harrad1 1; ;1University
ofBirmin
Birmin
OVERVIEW
OVERVIEW
SAMPLING
SAMPLING
Purpose:
Purpose:
Identification
Identification
of of
legacy
legacy
and
and
novel
novel
brominated
brominated
flame
flame
retardants
retardants
in in
dust
dust
samples
samples
onon
Thermo
Thermo
Scientific™
Scientific™
Quadrupole-Orbitrap™
Quadrupole-Orbitrap™
benchtop
benchtop
instrumentation.
instrumentation.
Sampling
Sampling
strategy
strategy
AllAll
dust
dust
samples
samples
were
were
taken
taken
in in
offices,
offices,
laboratories
laboratories
and
and
instrument
instrument
assembly
assembly
rooms
rooms
of of
thethe
Thermo
Thermo
Scientific
Scientific
Bremen
Bremen
factory
factory
site.
site.
The
The
samples
samples
were
were
collected
collected
according
according
to to
anan
established
established
protocol
protocol
[4].[4].
Shortly,
Shortly,
in in
offices
offices
1 1
m²m²
of of
carpet
carpet
was
was
vacuumed
vacuumed
forfor
2 2
min
min
and
and
in in
case
case
of of
bare
bare
floors
floors
4 4
m²m²
was
was
vacuumed
vacuumed
forfor
4 min.
4 min.
Samples
Samples
were
were
collected
collected
using
using
nylon
nylon
sample
sample
socks
socks
(25(25
µmµm
pore
pore
size)
size)
that
that
were
were
mounted
mounted
in in
thethe
furniture
furniture
attachment
attachment
tube
tube
of of
thethe
vacuum
vacuum
cleaner.
cleaner.
Prior
Prior
to to
analysis
analysis
samples
samples
were
were
stored
stored
in in
sealed
sealed
bags
bags
at at
4 㼻C.
4 㼻C.
Methods:
Methods:
Identification
Identification
and
and
screening
screening
of of
brominated
brominated
substances
substances
of of
interest
interest
was
was
conducted
conducted
in in
dust
dust
samples.
samples.
Results:
Results:Dust
Dustmight
mightbebea arelevant
relevantsource
sourceof ofbrominated
brominatedflame
flameretardants
retardantsand
andtherefore
therefore
interesting
interestingforforhuman
humanexposure.
exposure.HRAM
HRAMinstrumentation
instrumentationaids
aidsin inthetheidentification
identificationof ofthese
these
compounds.
compounds.
Figure
Figure
1. 1.
Schematic
Schematic
of ofselective
selective
extraction
extraction
using
using
Thermo
Thermo
Scientific
Scientific
ASE
ASE
extraction
extraction
cells
cells
INTRODUCTION
INTRODUCTION
Extraction
Extraction
Due
Due
to to
legislative
legislative
restrictions
restrictions
onon
manufacture
manufacture
and
and
use
use
of of
some
some
brominated
brominated
flame
flame
retardants
retardants
(BFRs),
(BFRs),
several
several
new
new
chemicals
chemicals
(NBFRs)
(NBFRs)
have
have
been
been
developed.
developed.
ToTo
explore
explore
their
their
presence
presence
in in
different
differentenvironmental
environmentalcompartments
compartmentsand
andultimately
ultimatelyunderstand
understandtheir
theirenvironmental
environmentalfate,
fate,
analytical
analytical
methods
methods
forfor
targeted
targeted
analysis
analysis
areare
required
required
[1].[1].
Classically
Classically
these
these
compounds
compounds
areare
determined
determined
byby
GC-based
GC-based
instrumental
instrumental
methods.
methods.
In In
recent
recent
years,
years,
LC-based
LC-based
methods
methods
coupled
coupled
to tolow
lowresolution
resolutionmass
massspectrometers
spectrometershave
havealso
alsobeen
beendeveloped
developed[2].[2].Advances
Advancesin inhigh
high
resolution
resolutionmass
massspectrometry
spectrometryfacilitate
facilitateaccurate
accuratemeasurements
measurementsand
andidentification
identificationof of
unknowns,
unknowns,including
includingdegradation
degradationand
andtransformation
transformationproducts.
products.Moreover,
Moreover,bromine
bromineisotopic
isotopic
pattern
pattern
analysis
analysis
asas
well
well
asas
thethe
use
use
of of
mass
mass
defect
defect
plots
plots
and
and
filters,
filters,
helps
helps
identify
identify
relevant
relevant
substances,
substances,with
withsuch
suchtechniques
techniquesstarting
startingto tobebemore
morecommonly
commonlyused
usedin inenvironmental
environmental
science
science
[3].[3].
Sample
Sample
and
and
Dispersant
Dispersant
Adsorbent
Adsorbent
added
added
toto
cell
cell
toto
retain
retain
interferences
interferences
MATERIALS
MATERIALSAND
ANDMETHODS
METHODS
Sample
Sample
Preparation
Preparation
0.50.5
g of
g of
dust
dust
was
was
weighed,
weighed,
spiked
spiked
with
with
mass-labeled
mass-labeled
TBBP-A
TBBP-A
and
and
mixed
mixed
with
with
diatomaceous
diatomaceous
earth
earth
asas
dispersant.
dispersant.
Extraction
Extraction
was
was
conducted
conducted
using
using
a Thermo
a Thermo
Scientific™
Scientific™
Dionex™
Dionex™
ASE™
ASE™
350
350
accelerated
accelerated
solvent
solvent
extractor
extractor
and
and
in-cell
in-cell
cleanup
cleanup
(Figure
(Figure
1).1).
Chemical
Chemical
adsorbents
adsorbents
silica
silica
and
andFlorisil™
Florisil™were
wereemployed
employedto toreduce
reducepossible
possiblematrix
matrixinterferences.
interferences.Extraction
Extractionsolvents
solvents
included
included
hexane,
hexane,
dichloromethane
dichloromethane
and
and
acetone.
acetone.
Samples
Samples
were
were
evaporated
evaporated
to to
dryness
dryness
using
using
a a
Thermo
ThermoScientific™
Scientific™Rocket™
Rocket™Evaporator
Evaporatorsystem
systemand
andthen
thenreconstituted
reconstitutedin in2 2mLmLof of
methanol:toluene
methanol:toluene
(1:1).
(1:1).
The
The
extraction
extraction
instrumentation
instrumentation
is is
shown
shown
in in
Figure
Figure
2. 2.
Figure
Figure
2. 2.
Thermo
Thermo
Scientific
Scientific
Dionex
Dionex
ASE
ASE
350
350
and
andThermo
Thermo
Scientific
Scientific
Rocket
Rocket
Evaporator
Evaporator
system
system
Liquid
Liquid
Chromatography
Chromatography
Final
Finalextracts
extractswere
wereseparated
separatedonona aThermo
ThermoScientific™
Scientific™Accucore™
Accucore™RP-MS
RP-MS100x2.1mm,
100x2.1mm,
2.6µm
2.6µm
column
column
onon
a Thermo
a Thermo
Scientific™
Scientific™
Accela™
Accela™
HPLC
HPLC
system
system
(Accela
(Accela
1250
1250
Pump
Pump
and
and
Open
Open
autosampler
autosampler– –Figure
Figure3),3),using
usinga a1616minutes
minutesgradient
gradientelution
elutionprogram
programwith
withwater
water(mobile
(mobile
phase
phase
A)A)
and
and
methanol
methanol
(mobile
(mobile
phase
phase
B)B)
at at
a flow
a flow
rate
rate
of of
400
400
µl/min.
µl/min.
The
The
gradient
gradient
started
started
at at
20%
20%
phase
phase
B, B,
was
was
ramped
ramped
to to
40%
40%
BB
in in
4 minutes,
4 minutes,
then
then
further
further
to to
100%
100%
BB
in in
5 minutes
5 minutes
and
and
was
was
held
held
forfor
3 minutes
3 minutes
at at
100%
100%
B.B.
Initial
Initial
conditions
conditions
were
were
restored
restored
within
within
0.10.1
minutes,
minutes,
with
with
a a
final
final
equilibration
equilibration
of of
4 minutes.
4 minutes.
Mass
Mass
Spectrometry
Spectrometry
Mass
Massspectrometric
spectrometricanalysis
analysiswas
wasrunrunonona aThermo
ThermoScientific™
Scientific™Q QExactive™
Exactive™hybrid
hybrid
quadrupole-Orbitrap™
quadrupole-Orbitrap™
mass
mass
spectrometer
spectrometer
(Figure
(Figure
3) 3)
with
with
anan
APCI
APCI
source,
source,
using
using
optimized
optimized
conditions.
conditions.
MS-parameter
MS-parameter
forfor
screening
screening
purposes
purposes
•Full
•Full
Scan
Scan
•APCI
•APCI
negative
negative
•R•R
= 70,000
= 70,000
at at
m/z
m/z
200
200
•m/z
•m/z
300–1000
300–1000
Data
Data
Analysis
Analysis
Raw
Rawdata
datafiles
fileswere
wereprocessed
processedusing
usingboth
bothThermo
ThermoScientific™
Scientific™Xcalibur™
Xcalibur™and
andThermo
Thermo
Scientific™
Scientific™Compound
CompoundDiscoverer™
Discoverer™software.
software.The
Theworkflow
workflowused
usedforforscreening
screeningof of
environmental
environmentalunknowns
unknownsis isshown
shownin inFigure
Figure4. 4.It Itincludes
includesthethedetection
detectionof ofunknowns
unknowns
compounds,
compounds,elemental
elementalcomposition
compositionpredictions,
predictions,hides
hidesbackground
backgroundfrom
fromblanks,
blanks,performs
performsa a
ChemSpider
ChemSpider
library
library
search
search
and
and
scores
scores
thethe
compounds
compounds
based
based
onon
selected
selected
bromine
bromine
isotope
isotope
patterns.
patterns.
In Inaddition,
addition,mass
massdefect
defectplots
plotswere
werecreated
createdusing
usingMicrosoft™
Microsoft™Excel™
Excel™to tovisualize
visualizethethe
presence
presence
of of
brominated
brominated
compounds.
compounds.
These
These
chemicals
chemicals
have
have
a aunique
unique
negative
negative
mass
mass
defect,
defect,
which
whichreadily
readilydistinguishes
distinguishesthem
themfrom
fromother
othermolecules
moleculesin ina acomplex
complexmass
massspectrum.
spectrum.One
One
mass
mass
scale
scale
applicable
applicable
to to
environmental
environmental
analytical
analytical
chemistry
chemistry
is is
defined
defined
byby
thethe
substitution
substitution
of of
a a
hydrogen
hydrogen
atom
atom
byby
a a
chlorine
chlorine
atom
atom
(H/Cl).
(H/Cl).
In In
analogy
analogy
to to
thethe
Kendrick
Kendrick
mass
calculation,
thethe
mass
calculation,
conversion
used
here
is is
based
onon
thethemultiplication
of of
conversion
used
here
based
multiplication
each
each
peak
peak
of of
a chosen
a chosen
mass
mass
spectrum
spectrum
byby
34/33.96102
34/33.96102
and
and
plotting
plotting
thethe
nominal
nominal
mass
mass
vs.vs.
thethe
transformed
transformed
mass
mass
defect.
defect.
Figure
3. 3.
QQ
Exactive
with
Thermo
Scientific
Accela
1250
Pump
and
Open
autosampler
Figure
Exactive
with
Thermo
Scientific
Accela
1250
Pump
and
Open
autosampler
Figure 3. Q Exactive with Thermo Scientific Accela 1250 Pump and Open autosampler
identification
of compounds
andconfirming
unknownscriteria
by means
selectivity,
elemental
compositions
suspect
the following
were ofselected:
spectral
similarity
score (SFit>80%)
and isotopic
scoring.
The use of
databases, was
suchconducted
as ChemSpider,
help
andpattern
accurate
mass deviation
< 5relevant
ppm. Confirmation
throughcan
the measurement
identify compounds.
of reference standards where available. However additional MS/MS measurements might be
d
d
Figure 3. Q Exactive with Thermo Scientific Accela 1250 Pump and Open autosampler
needed. The use of high-resolution accurate mass (HRAM) instrumentation facilitates
Figure 5.identification
Mass defectof
plot
of dust sample
transformed
with H/Cl
scale 34 / 33.96102
compounds
and unknowns
by means
of selectivity,
elemental scale
compositions
and isotopic pattern scoring. The use of relevant databases, such as ChemSpider, can help
identify compounds.
BEH-TBP
EH-TBB
Figure 5. Mass
defect plot of dust sample transformed with H/Cl scale 34 / 33.96102 scale
HBCD
TBBPA
o
f
s
a
e
EH-TBB
penta
DBDPE
BEH-TBP
hexa
hepta HBCD
octa
TBBPA
nona
deca
BDE
vel brominated flame retardants using a Q Exactive H
DBDPE
penta
hexa
hepta
octa
nona
deca
BDE
e
,
e
a
e
m
mingham, School of Geography, Earth and Environmental Sciences, Birmingham, United Kingdom 2Therm
vel brominated flame retardants using a Q Exactive H
2Therm
Figure 4. Workflow of the environmental unknown screening using Thermo Scientific
Selected
compounds are Birmingham,
shown in Table 1 and Figure
6. The formation
of different quasimingham,
School of Geography, Earth and Environmental
Sciences,
United
Kingdom
Compound Discoverer
molecular ions in APCI for these compounds has been reported in literature. Here, the most
Figure 4. Workflow of the environmental unknown screening using Thermo Scientific
Compound Discoverer
intense ions are shown. Compounds detected in the screening include:
2-ethylhexyltetrabromobenzoate
(EH-TBB), decabromodiphenyl ethane (DBDPE), bis(2ethylhexyl)tetrabromophtalate
(BEH-TBP),
tetrabrombisphenol
A
(TBBP-A)
and
hexabromcyclododecane (HBCD), in addition to the afore mentioned PBDEs.
Selected compounds are shown in Table 1 and Figure 6. The formation of different quasimolecular ions in APCI for these compounds has been reported in literature. Here, the most
intense ions are shown. Compounds detected in the screening include:
Table 1. Selected (N)BFRs in dust sample
2-ethylhexyltetrabromobenzoate
(EH-TBB), decabromodiphenyl ethane (DBDPE), bis(2ethylhexyl)tetrabromophtalate
(BEH-TBP),quasi-molecular
tetrabrombisphenol
A
(TBBP-A)
and
ion
∆ m/z
hexabromcyclododecane
(HBCD), in addition to the afore mentioned PBDEs.
Time (min)
Suspect compound
Formula
and m/z
EH-TBB
Table 1.
C15H18Br4O2
[M-Br+O]Selected (N)BFRs
in dust sample
BEH-TBP
C24H34Br4O4
(ppm)
484.87706
[M-C8H17+H-Br]512.87402
quasi-molecular
ion
0.08
10.24
0.98
∆ m/z
0.82
(ppm)
11.16
Time (min)
12.06
Suspect compound
DBDPE
Formula
C14H4Br10
[M-Br+O]-
TBBP-A
EH-TBB
C15H12Br4O2
C15H18Br4O2
[M-H][M-Br+O]-
542.74571
484.87706
0.09
0.08
8.30
10.24
HBCD
BEH-TBP
C12H18Br6
C24H34Br4O4
[M-H][M-C8H17+H-Br]-
640.63746
512.87402
0.23
0.98
9.02
11.16
and m/z
906.28362
Compounds:
(EH-TBB),
(BEH-TBP),12.06
DBDPE (2-ethylhexyltetrabromobenzoate
C14H4Br10
[M-Br+O]- bis(2-ethylhexyl)tetrabromophtalate
906.28362
0.82
decabromodiphenyl ethane (DBDPE), tetrabrombisphenol A (TBBP-A), hexabromcyclododecane (HBCD)
TBBP-A
RESULTS
Method
The use of different extraction solvent mixtures was investigated to obtain the optimal
extraction results. A mixture of hexane:dichloromethane (3:1) showed better extraction results
compared to hexane:acetone (3:1) – compare Figure 7 (TBBP-A). Other chemical adsorbents,
such as copper, alumina or activated carbon might need to be included in the in-cell cleanup
depending on the complexity of the matrix. Dust samples collected in the instrument assembly
Method
rooms
showed to contain more brominated compounds, compared to dust taken in offices and
The use ofThis
different
extraction
was presence
investigated
to obtain equipment
the optimal
laboratories.
is most
probably solvent
due to mixtures
the increased
of electronic
extractionflame
results.
A mixture
of hexane:dichloromethane
(3:1) showed better extraction results
containing
retardants
in these
areas.
compared to hexane:acetone (3:1) – compare Figure 7 (TBBP-A). Other chemical adsorbents,
suchdefect
as copper,
Mass
plot alumina or activated carbon might need to be included in the in-cell cleanup
theestimate
complexity
of the
matrix.
samples
collected inwithin
the instrument
assembly
Todepending
obtain an on
initial
of the
number
of Dust
brominated
compounds
the dust samples,
rooms
showed
to contain
more brominated
compounds,
compared
to dust
taken inpattern
offices of
and
mass
defect
plots
were calculated
and plotted
as shown
in Figure
5. Isotopic
laboratories.
is most probably
due
to the polybrominated
increased presence
of electronic
equipment
compounds
canThis
be recognized.
As an
example
diphenyl
ethers (PBDEs)
–
containing
flame
retardants
in
these
areas.
penta through deca - are plotted all in one band and separated by 79 Da increments, i.e.
RESULTS
C15H12Br4O2
[M-H]-
Figure 7. Results for HBCD (top) and TBBPA (bottom) in Compound Discoverer
of reference standards where available. However additional MS/MS measurements might be
Screening
needed.
The use of high-resolution accurate mass (HRAM) instrumentation facilitates
fraction of
The suspect
using Compound
showed
a large
identification
of screening
compoundsresults
and unknowns
by meansDiscoverer
of selectivity,
elemental
compositions
brominated
flame retardants
in use
the samples,
legacy BFRs,
asChemSpider,
well as NBFRs.
For a
and isotopic pattern
scoring. The
of relevantboth
databases,
such as
can help
suspect
the following confirming criteria were selected: spectral similarity score (SFit>80%)
identify
compounds.
and accurate mass deviation < 5 ppm. Confirmation was conducted through the measurement
of reference
where
available.
However
additional
measurements
might
be
Figure
5. Massstandards
defect plot
of dust
sample
transformed
withMS/MS
H/Cl scale
34 / 33.96102
scale
needed. The use of high-resolution accurate mass (HRAM) instrumentation facilitates
identification of compounds and unknowns by means of selectivity, elemental compositions
and isotopic pattern scoring. The use of relevant databases, such as ChemSpider, can help
BEH-TBP
identify compounds.
EH-TBB
HBCD
Figure 5. Mass defect plot of dustTBBPA
sample transformed with H/Cl scale 34 / 33.96102 scale
DBDPE
EH-TBB
TBBPA
hepta
octa
nona
deca
BDE
HBCD
DBDPE
penta
hexa
hepta
octa
nona
deca
0.09
8.30
Figure
7. Results
for HBCD
(top) and
TBBPA
Compound
In addition,
Compound
Discoverer
allows
for (bottom)
unknowninscreening
withDiscoverer
unbiased peak detection
within defined elemental composition ranges. Hereby additional halogenated compounds of interest
that have not come to attention yet can be identified, as well as possible transformation products
identified.
corresponding to the mass of bromine minus a hydrogen atom.
Mass defect plot
To obtain an initial estimate of the number of brominated compounds within the dust samples,
Screening
mass
defectscreening
plots wereresults
calculated
plotted as
shown inshowed
Figure 5.
patternofof
The
suspect
usingand
Compound
Discoverer
a Isotopic
large fraction
compounds
can retardants
be recognized.
an example
diphenyl
(PBDEs)
brominated
flame
in theAs
samples,
both polybrominated
legacy BFRs, as
well asethers
NBFRs.
For a –
penta
through
deca
are
plotted
all
in
one
band
and
separated
by
79
Da
increments,
i.e.
suspect the following confirming criteria were selected: spectral similarity score (SFit>80%)
corresponding
to the
mass of< bromine
minus a hydrogen
atom.
and
accurate mass
deviation
5 ppm. Confirmation
was conducted
through the measurement
penta BEH-TBP
hexa
542.74571
In addition,
Compound Discoverer
for unknown screening
detection
HBCD
C12H18Br6 allows
[M-H]640.63746with unbiased
0.23 peak 9.02
within defined elemental composition ranges. Hereby additional halogenated compounds of interest
that
have not(2-ethylhexyltetrabromobenzoate
come to attention yet can be(EH-TBB),
identified,
as well as possible transformation
products
Compounds:
bis(2-ethylhexyl)tetrabromophtalate
(BEH-TBP),
decabromodiphenyl ethane (DBDPE), tetrabrombisphenol A (TBBP-A), hexabromcyclododecane (HBCD)
identified.
BDE
2 Method Development for the Identification of Bovel Brominated Flame Retardants Using a Q Exactive HRAM Mass Spectrometer
5
Compounds: (2-ethylhexyltetrabromobenzoate (EH-TBB), bis(2-ethylhexyl)tetrabromophtalate (BEH-TBP),
decabromodiphenyl ethane (DBDPE), tetrabrombisphenol A (TBBP-A), hexabromcyclododecane (HBCD)
In addition,
Discoverer
allowsinfordust
unknown
FigureCompound
6. XIC of selected
(N)BFRs
samplescreening with unbiased peak detection
within defined
elemental
composition ranges.
Hereby
additional halogenated compounds of interest
C:\ELUTE\13
Nov 2015 - dust\ACE_1
11/13/15
19:42:10
that have not come to attention yet can be identified, as well as possible transformation products
RT:4.96 - 14.09
SM:7B
identified.
NL:
10.24
100
5 ppm mass tolerance
EH-TBB [M-Br+O]-
50
Figure 7. Results for HBCD (top) and TBBPA (bottom) in Compound Discoverer
0
100
11.16
BEH-TBP [M-C8H17+H-Br]-
50
12.08
DBDPE [M-Br+O]-
50
0
100
mo Fisher Scientific, Bremen,
Germany
TBBPA [M-H]50
0
100
50
9.26
HBCD [M-H]-
Figure
6. XIC of selected (N)BFRs in dust sample
0
C:\ELUTE\13
5 Nov 20156- dust\ACE_17
RT:4.96 - 14.09
SM:7B
100
8 11/13/15 19:42:10
9
10
Time (min)
11
12
13
10.24
5 ppm mass tolerance
EH-TBB [M-Br+O]-
50
CONCLUSIONS
0
11.16
REFERENCES
0
100
9.02
14
NL:
1.01E4
m/z=
484.87669484.88153
MS ACE_1
NL:
m/z=
542.74300542.74842
MS ACE_1
NL:
2.55E5
m/z=
1. Covaci, A., et al., Novel brominated flame retardants: a review of their analysis, environmental
640.63316HBCD
50 fate and behaviour. Environment International,
640.63956
2011. [M-H]37(2): p. 532-56.
9.26
MS ACE_1
2.0 Zhou, S.N., et al., Development of liquid chromatography atmospheric pressure chemical
mass spectrometry
of halogenated
in
5ionization6 tandem 7
8
9 for analysis
10
11
12flame retardants
13
14 wastewater.
Time (min)
Analytical and Bioanalytical Chemistry, 2010.
396(3): p. 1311-20.
3. Jobst, K.J., et al., The use of mass defect plots for the identification of (novel) halogenated
contaminants in the environment. Analytical and Bioanalytical Chemistry, 2013. 405(10): p. 328997.
4. Abdallah, M.A., S. Harrad, and A. Covaci, Hexabromocyclododecanes and TetrabromobisphenolA inlegacy
IndoorBFRs
Air and
in Birmingham,
UK -inImplications
for This
Human
Exposure.
Environmental
Several
andDust
NBFRs
were identified
dust samples.
indicates
the relevance
of
& Technology,
2008.
p. 6855–6861.
dust Science
containing
chemicals as
an 42:
entry
pathway to human and environmental exposure. Further
14
1. Covaci, A., et al., Novel brominated flame retardants: a review of their analysis, environmental
fate and behaviour. Environment International, 2011. 37(2): p. 532-56.
2. Zhou, S.N., et al., Development of liquid chromatography atmospheric pressure chemical
ionization tandem mass spectrometry for analysis of halogenated flame retardants in wastewater.
Analytical and Bioanalytical Chemistry, 2010. 396(3): p. 1311-20.
3. Jobst, K.J., et al., The use of mass defect plots for the identification of (novel) halogenated
contaminants in the environment. Analytical and Bioanalytical Chemistry, 2013. 405(10): p. 328997.
4. Abdallah, M.A., S. Harrad, and A. Covaci, Hexabromocyclododecanes and TetrabromobisphenolA in Indoor Air and Dust in Birmingham, UK - Implications for Human Exposure. Environmental
Science & Technology, 2008. 42: p. 6855–6861.
ACKNOWLEDGEMENTS
The research leading to these results has received funding from the People Programme (Marie Curie
Actions) of the European Union‘s Seventh Framework Programme FP7/2007-2013/ under REA grant
agreement n㼻606857.
TRADEMARKS/LICENSING
© 2016 Thermo Fisher Scientific Inc. All rights reserved. Florisil is a trademark of U. S. Silica
Company. ChemSpider is a trademark of the Royal Society of Chemistry. Microsoft and Excel are
registered trademarks of Microsoft Corporation. All other trademarks are the property of Thermo
Fisher Scientific and its subsidiaries. This information is not intended to encourage use of these
products in any manners that might infringe the intellectual property rights of others.
studies to elucidate the environmental fate, especially of the novel compounds, have to be
conducted.
ACKNOWLEDGEMENTS
Mass defect plots are a useful instrument to greatly simplify any chosen mass spectrum. Compound
The research leading to these results has received funding from the People Programme (Marie Curie
Discoverer is a powerful tool for unknown screening and structural identification of compounds in
Actions) of the European Union‘s Seventh Framework Programme FP7/2007-2013/ under REA grant
environmental sciences.
agreement n㼻606857.
REFERENCES
TRADEMARKS/LICENSING
1. Covaci, A., et al., Novel brominated flame retardants: a review of their analysis, environmental
© 2016 Thermo Fisher Scientific Inc. All rights reserved. Florisil is a trademark of U. S. Silica
fate and behaviour. Environment International, 2011. 37(2): p. 532-56.
Company. ChemSpider is a trademark of the Royal Society of Chemistry. Microsoft and Excel are
2. Zhou, S.N., et al., Development of liquid chromatography atmospheric pressure chemical
registered trademarks of Microsoft Corporation. All other trademarks are the property of Thermo
ionization tandem mass spectrometry for analysis of halogenated flame retardants in wastewater.
Fisher Scientific and its subsidiaries. This information is not intended to encourage use of these
Analytical and Bioanalytical Chemistry, 2010. 396(3): p. 1311-20.
products in any manners that might infringe the intellectual property rights of others.
3. Jobst, K.J., et al., The use of mass defect plots for the identification of (novel) halogenated
contaminants in the environment. Analytical and Bioanalytical Chemistry, 2013. 405(10): p. 328997.
4. Abdallah, M.A., S. Harrad, and A. Covaci, Hexabromocyclododecanes and TetrabromobisphenolA in Indoor Air and Dust in Birmingham, UK - Implications for Human Exposure. Environmental
Science & Technology, 2008. 42: p. 6855–6861.
ACKNOWLEDGEMENTS
The research leading to these results has received funding from the People Programme (Marie Curie
Actions) of the European Union‘s Seventh Framework Programme FP7/2007-2013/ under REA grant
agreement n㼻606857.
TRADEMARKS/LICENSING
© 2016 Thermo Fisher Scientific Inc. All rights reserved. Florisil is a trademark of U. S. Silica
Company. ChemSpider is a trademark of the Royal Society of Chemistry. Microsoft and Excel are
registered
trademarks of Microsoft Corporation. All other trademarks are the property of Thermo
www.thermofisher.com
Fisher Scientific and its subsidiaries. This information is not intended to encourage use of these
©2016 Thermo
Scientific
All rights
reserved.
Florisil is a trademark
U. S. Silica
Company. ChemSpider is a trademark
products
in any Fisher
manners
thatInc.
might
infringe
the intellectual
propertyofrights
of others.
of the Royal Society of Chemistry. Microsoft and Excel are registered trademarks of Microsoft Corporation ISO is a trademark of the
International Standards Organization. All other trademarks are the property of Thermo Fisher Scientific and its subsidiaries. This
information is presented as an example of the capabilities of Thermo Fisher Scientific products. It is not intended to encourage use
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REFERENCES
7.35E4
m/z=
TBBPA [M-H]-
11
NL:
7.35E4
m/z=
906.27909906.28815
MS ACE_1
Mass
defect plots are a useful instrument
to greatly
simplify any chosen mass spectrum.906.27909Compound
50
906.28815
DBDPE
[M-Br+O]MS ACE_1
Discoverer is a powerful tool for unknown screening and structural identification of compounds
in
0
NL:
8.30
environmental
sciences.
100
1.56E4
50
10
Time (min)
Mass defect plots are a useful instrument to greatly simplify any chosen mass spectrum. Compound
Discoverer is a powerful tool for unknown screening and structural identification of compounds in
environmental sciences.
100
1.04E5
Several
legacy BFRs and NBFRs were identified in dust samples. This indicates the relevance
of
m/z=
512.87146dust
containing chemicals
as an entry
pathway to human and environmental exposure.
Further
BEH-TBP
[M-C8H17+H-Br]50
512.87658
ACE_1to be
studies to elucidate the environmental fate, especially of the novel compounds, MS
have
0
conducted.
NL:
12.08
100
9
NL:
1.04E5
m/z=
512.87146512.87658
MS ACE_1
NL:
2.55E5
m/z=
640.63316640.63956
MS ACE_1
9.02
8
Several legacy BFRs and NBFRs were identified in dust samples. This indicates the relevance of
dust containing chemicals as an entry pathway to human and environmental exposure. Further
studies to elucidate the environmental fate, especially of the novel compounds, have to be
conducted.
NL:
1.56E4
m/z=
542.74300542.74842
MS ACE_1
8.30
7
1.01E4
m/z=
484.87669484.88153
MS ACE_1
HRAM mass spectrometer
0
100
6
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