Talanta 167 (2017) 411–427

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Talanta
journal homepage: www.elsevier.com/locate/talanta

Quantification of polybrominated diphenyl ethers (PBDEs) in food. A review MARK

⁎
Wojciech Jerzy Pietroń , Paweł Małagocki
Radiobiology Department, National Veterinary Research Institute (NVRI), 57 Partyzantow, 24-100 Pulawy, Poland

A R T I C L E I N F O A BS T RAC T

Keywords: The polybrominated diphenyl ethers (PBDEs), a class of brominated flame retardants (BFRs), are food
Polybrominated diphenyl ethers contaminants of animal origin. Interest in food matrices analysis is growing due to the toxicity of PBDEs and
Extraction techniques European Commission (EC) recommendation (118/2014/EU). Here we review papers concerning methods of
Food samples PBDEs analysis while focusing on extraction, clean up, chromatographic separation and detection techniques.
Brominated flame retardants
The emphasis is put on EC recommendation, the congeners and the efficiency of different detection systems.
PBDEs quantification
PBDEs
Some analytical problems caused by differences between low- and high-molecular-mass congener properties,
especially the possible limitations of BDE-209 analysis, are discussed. Detection techniques and mass
spectrometry (MS) ionization modes applied to PBDE level determination in food of animal origin are
compared. The gas chromatography (GC) coupled to high-resolution MS is undoubtedly fit for that purpose, but
ion trap MS could be used to PBDEs determination as well. ECD is the most sensitive technique; however, other
halogen compounds present in sample may interfere with PBDEs congeners necessitating results confirmation.
Moreover, the novel atmospheric pressure chemical ionization (APCI) method applied to GC in tandem with MS
places this technique in the top category of the most sensitive techniques which may be used.

1. Introduction
Risk control of food contaminants hazardous to human health is
one of the biggest challenges for food safety authorities and at the same
time for analytical laboratories. In the last decade polybrominated
diphenyl ethers (PBDEs), a group of persistent organic pollutants
(POPs) have been included among the substances of particular interest.
PBDEs, applied as brominated flame retardants (BFRs) since 1960 and
added to the class of commercial products since 1965, superseded
polybrominated and polychlorinated biphenyls (PBBs and PCBs) with-
drawn in the 1970s and quickly became the most popular BFRs [1,2].
The total amount of commercial decaBDE produced between 1970 and
2005 was estimated at 1.1–1.25 million tonnes and is considered to be
about 75% of the world PBDEs production [3]. PBDEs were used as
additives (5–30% by weight) to plastic, furniture, textiles, electric cable
insulation, water and sewage pipes, office equipment and electronic
devices to prevent and retard the spread of fire [4]. There are 209
possible PBDE congeners numbered according to the International
Union of Pure and Applied Chemistry (IUPAC) system analogously to
polychlorinated biphenyls (Table 1). Their structural model is shown in
Fig. 1.
1.1. PBDEs hazard
PBDEs are released into the environment by abrasion of the
polymer during its life cycle and release is accelerated by heating and
PBDEs are transported with dust [5–8]. From this point of view,
existing products containing PBDEs are a reservoir of these POPs.
Uncontrolled burning of plastic also contributes to the emissions when
PBDEs remain in the ashes and more toxic chemicals, e.g. polybromi-
nated dibenzofurans and dibenzo-p-dioxins (PBDD/Fs) are generated
[9–11]. Moreover, sediments from sewage treatment plants used as

Abbreviations: ACS, automatic cleanup system; APCI, Atmospheric Pressure Chemical Ionization; APPI, Atmospheric Pressure Photo Ionization; b.w., body weight; BFRs, brominated
flame retardants; d.w., dry weight; ECD, electron capture detector; ECNI, electron capture negative ionization; EI, electron ionization; GC, gas chromatography; GPC, gel permeation
chromatography; HBCDDs, hexabromocyclododecanes; HRMS, high resolution mass spectrometry; ICP, Inductively Coupled Plasma; IDMS, isotopic dilution mass spectrometry; iLOD,
instrumental detection limits; IT, Ion Trap; IUPAC, International Union of Pure and Applied Chemistry; l.w., lipid weight; LC, liquid chromatography; LOD, limit of detection; LOQ,
limit of quantification; LRMS, low resolution mass spectrometry; MAE, Microwave-Assisted Extraction; MeTBBP-A, tetrabromobisphenol-A dimethyl ether; MS, mass spectrometry;
MS-MS, tandem mass spectrometry; MSPD, Matrix Solid Phase Dispersion; NCI, negative chemical ionization; PAHs, Polycyclic aromatic hydrocarbon; PBBs, polybrominated
biphenyls; PBDDs, polybrominated dioxins; PBDEs, polybrominated diphenyl ethers; PBDFs, polybrominated furans; PCBs, polychlorinated biphenyls; PCDE, polychlorinated diphenyl
ethers; PCNs, polychlorinated naphthalenes; PCTs, polychlorinated terphenyls; PLE, Pressurized Liquid Extraction; POPs, persistent organic pollutants; PTV, programmable
temperature vaporization; SEC, size exclusion chromatography; SPE, solid phase extraction; TBBP-A, tetrabromobisphenol-A; TOF, time-of-flight; USAL, Ultrasound-Assisted Leaching;
w.w., wet weight
⁎
Corresponding author.
E-mail addresses: wojciech.pietron@piwet.pulawy.pl (W.J. Pietroń), pawel.malagocki@piwet.pulawy.pl (P. Małagocki).

http://dx.doi.org/10.1016/j.talanta.2017.02.043
Received 7 November 2016; Received in revised form 16 February 2017; Accepted 19 February 2017
Available online 21 February 2017
0039-9140/ © 2017 Elsevier B.V. All rights reserved.
W.J. Pietroń, P. Małagocki Talanta 167 (2017) 411–427

Table 1 be an effect of UV irradiation of PBDEs, but the low efficiency of this

Basic information about PBDEs. reaction in the aquatic environment does not explain the observed
concentrations of OH-PBDEs and PBDD/Fs in biota, e.g. fish
Br atoms Homologues Possible IUPAC Molecular Molecular
group congeners numbers formula mass [10,37,38]. OH-PBDEs are naturally produced by some algae species,
when polybrominated phenols are precursors [39]. There is also a
1 monoBDE 3 1–3 C12H9Br1O 249.1 metabolic relationship between PBDEs, hydroxylated PBDEs and
2 diBDE 12 4–15 C12H8Br2O 328.0
methoxylated PBDEs, and differences in the profiles of those com-
3 triBDE 24 16–39 C12H7Br3O 406.9
4 tetraBDE 42 40–81 C12H6Br4O 485.8 pounds in apical sea predators (tuna, polar bear, albatross) suggest
5 pentaBDE 46 82–127 C12H5Br5O 564.7 interspecies variability in PBDEs accumulation or metabolism [40].
6 hexaBDE 42 128–169 C12H4Br6O 643.6 Hydroxylated PBDEs demonstrate endocrine and neurological toxici-
7 heptaBDE 24 170–193 C12H3Br7O 722.5 ties as well as a potential for genotoxicity and the development of lung
8 octaBDE 12 194–205 C12H2Br8O 801.4
cancer [32,41,42]. Studies have demonstrated the harmful nature of
9 nonaBDE 3 206–208 C12H1Br9O 880.3
10 decaBDE 1 209 C12Br10O 959.2 the PBDEs in biota; furthermore, future research should take into
account interactions with other environmental contaminants [2].

O 1.2. Means to improve food safety

The determination of environmental and food contamination levels

is important to estimate human exposure. PBDEs omnipresence in the
environment, accumulation potential and toxicity have led to the
Brm Brn inclusion of six congeners (BDE-47, 99, 153, 154, 175, 183) into the
POPs list of the Stockholm Convention. Consequently, the process of
Fig. 1. General structure of PBDEs, where n and m=0–5 and 1≤m+n ≤10.
worldwide PBDEs withdrawal has begun [32,43]. Control of PBDEs
concentrations in food would be more feasible to implement than the
fertilizers can cause secondary pollution of soil [12,13]. The chemical
reduction of its concentrations in dust. According to the European
properties which characterize PBDEs as hydrophobic compounds
Commission recommendation 2014/118/EU, ten PBDE congeners
(logKow values 5.9−10) exhibit potential to accumulate in animal
(BDE-28, 47, 49, 99, 100, 138, 153, 154, 183 and 209) should be
tissues [14,15]. Adsorption of PBDEs from the environment has also
analyzed using analytical methods with a limit of quantification (LOQ)
been demonstrated for some plant species [16,17] and earthworms
not higher than 0.01 ng/g fresh weight in food of animal origin,
[18]. The biota-soil accumulation factors (BSAFs) decrease with
products for specific nutritional uses and food for infants and small
increasing logKow of PBDEs [19]. Kierkegaard et al. suggest that
children [44].
polluted sewage silage may be the major source of PBDEs for cows
Thousands of articles concerning the determination and occurrence
[20,21].
of PBDEs in environmental samples have been published and the
Food of animal origin and house dust are the two main sources of
number of papers considering this subject in food-related matrices is
human exposure to PBDEs, anyway, its relative contribution to overall
constantly increasing. The aim of this paper is to compare novel
intake differs between countries. In the US, total daily intake is
methods of PBDEs analysis in food of animal origin focusing on
estimated at 7.1 ng/kg body weight (b.w.) per day, and in Germany
detection techniques.
0.29 ng/kg b.w. The estimated intake with dust can vary by three
orders of magnitude, while dietary intake is more convergent world-
2. Analytical methods
wide and is dominating the total intake in many countries. It should be
noted that dust can be an important route of exposure especially for
The search for “PBDE analysis” and “food” on Science Direct yields
toddlers and small children. [5–8,22–27]. The estimated average daily
over 3000 results. Reviewing such a popular topic required the authors
intake for adults through diet is 4.0 ng/kg b.w. per day in Europe
to adopt some rules for the selection of papers. We decided to compare
according to EFSA, and 0.6 ng/kg b.w. per day for the US population
the methods applied to PBDEs determination in food of animal origin
according to EPA [25,26]. Fish and fishery products are among the
and to omit the articles focusing on unchanged or slightly modified
most PBDEs contaminated foods and the concentration of congeners in
previously published methods. Analytical details of the methods
fish increases with fat content, similarly to other POPs [26,28]. PBDEs
presented in the selected papers are shown in Table 2. The type of
concentrations in the milk of breastfeeding mothers confirms the
matrices, sample pretreatment, analytical sample weight, solvent and
accumulation in the food chain and directly translates into a significant
techniques of extraction, clean up and detection were investigated. To
exposure of infants [26,29,30].
allow for critical comparison, the methods were sorted according to the
PBDEs exhibit low oral acute toxicity (LD50s > 5 g/kg b.w. rat).
detection technique.
However, the predictable half-life of PBDEs in the human body ranges
Although 209 PBDE congeners exist, the determination of indivi-
between 15 days to even 11.7 years, depending on congener structure
dual ones is related to their occurrence and availability of standards.
and the degree of bromination [22,31]. Available data demonstrate that
The EPA 1614 method allows for the determination of the majority of
PBDEs influence thyroid and sex hormones levels and cause chronic
PBDE congeners; however, its application requires a time consuming
toxic action against the central nervous and reproductive systems [32].
set-up and expensive equipment [45]. The papers selected focused
PBDEs mixtures display an immunomodulating effect, altering cyto-
mainly on 17 congeners: BDE-17, 28, 47, 49, 66, 71, 77, 85, 99, 100,
kine secretion by human peripheral blood mononuclear cells [33].
119, 126, 138, 153, 154, 183 and 209. This group contains ten PBDEs
Exposure to PBDEs increases the time to pregnancy in women trying to
from the EC 2014/118 recommendation. The range of matrices
get pregnant, decreases infant birth weight, and causes attention,
investigated was wide, but the most commonly studied were focused
motor coordination and cognitive function deficits in early school-age
on fish and other seafood products, the most contaminated food
children [14,32]. BDE-209 is relatively non-toxic [34], but data
category according to the EFSA report [26].
suggests the possibility of its debromination to more biologically active
Sampling, preparation and protection against cross-contamination
congeners [35,36]. However, there is no consensus about the fate of
or degradation of analyte are critical, especially when PBDEs are
PBDEs in the environment. Some data suggests PBDEs transformation
sensitive to sunlight [38]. In the majority of methods, water is removed
to PBDD/Fs via cyclization of hydroxylated PBDEs. Hydroxylation may
from samples by freeze-drying or with anhydrous sodium sulfate (VI).

412
 Table 2
Selected papers concerning PBDEs determination in food of animal origin.

Year Main/first Matrix Sample pre- Sample weight Extraction technique Extraction solvent Clean up Detection Number of Nr.
author treatment method citation*

2001 Alaee M. Lake trout, Herring, – 10 g w.w. Column extraction with DCM GPC HRMS 62 [77]
Sockeye salmon Na2SO4 deactivated silica gel
W.J. Pietroń, P. Małagocki

2002 Huwe J.K. Chicken fat – 1g - – EPA Method 1613 LRMS 55 [75]
modification,
Hx: H2SO4 digested
ACS
2002 Jacobs, M. N. Salmon, fish oil – 10 g w.w. Na2SO4 75 ml Hx:DCM:Actone 2 x SPE acid/neutral silica gel: LRMS 156 [47]
Soxhlet 2 h (3:1:1 v+v+v) deactivated alumina
2003 Pirard C. Fortified beef fat – 1g - – ACS IT 49 [78]
2003 de Boer J. Flounder, bream, marine – 100 g w.w. Na2SO4 Hx/acetone (3:1 v+v) 70 oC GPC, LRMS [10]
mussels, freshwater mussels Soxhlet 12 h H2SO4 digestion,
silica gel column
2003 Voorspoels S. Benthic invertebrates, – 1–10 g w.w. Na2SO4 Hx:Acetone (3:1 v+v) Jacobs, M. N., 2002 LRMS 135 [43]
benthic fish, benthic flatfish, Soxhlet 2,5 h
gadoid fish
2004 Fernandes A. Food Freeze-drying equivalent of up to Solvent extraction Hx Multi-layer silica connected HRMS 46 [41]
10 l.w. with carbon column;
Silica and alumina mini
columns
2004 Papke O. Fish, meat, – 10–100 g w.w. Na2SO4 Cyclohexane: DCM Drying on sodium sulphate, HRMS [21]
Solvent extraction acid digestion, activated silica
gel, alumina.
2005 Johnson-Restrepo Nine species of marine fish, – 20 g or 3 g l.w. Na2SO4 DCM:Hx Multi-layer silica HRMS/ECD [51]
B. dolphins Soxhlet 16 h (3:1 v+v)

413
2006 Labandeira A. Carp Freeze- drying 1 g d.w. Ground with alumina 2:1 DCM:Hx During extraction LRMS [62]
w+w
ASE
2006 Liu H. Fish tissue Freeze- drying – Acid silica DCM:Hx Silica gel with AgNO3 HRMS 33 [48]
Soxhlet 24 h
2006 Gómara B. Diary, eggs, Freeze- drying 6 g d.w. MSPD with silica gel Acetone: Hx Acid silica and basic alumina IT/ECD 54 [73]
sea fish, columns
shellfish, meat
2007 Akutsu K. 125 types of food – 5 g w.w. Digested with 1 M KOH Hx Acid silica gel LRMS 9 [39]
by 2 h
LLE
2007 Luo Q. Carp, grass carp, silver carp, Freeze- drying 1–5 g d.w. Na2SO4 DCM: Acetone H2SO4 digestion, acid silica and IT/LRMS 28 [27]
mud carp, carp Soxhlet 12 h alumina columns
2007 Pulkrabová J. Fish: chub, barbel, bream, – 30 g w.w. Na2SO4 Hx:DCM GPC; H2SO4 digestion LRMS 11 [50]
perch, and trout Soxhlet 8 h
2008 Shaw S.D. Harbor seals blubber – 5g + Na2SO4 Hx:DCM ACS HRMS/LRMS 25 [42]
+ silica gel
2008 Tapie N. Trout, eel, mysids Freeze- drying 0.5 g d.w. MAE 30 W 10 min DCM Filtration 5 x shaking with ECD 21 [44]
purification with sulffuric H2SO4; silica gel
acid)
2008 Wang D. Seals blubber Freeze- drying 2 g d.w. ASE + Na2SO4 Hx:DCM Multi-layer silica column IT/ECD 11 [58]
2009 Losada S. Trout, salmon and horse Freeze- drying 0.5 g d.w. +10 g Na2SO4 Hx:DCM During extraction IT 19 [56]
mackerel + 25 g Florisil (9:1 v+v)
ASE
2010 Li Y.F. Pig muscle, fat, liver and small Freeze- drying 0.5–8 g w.w. Soxhlet 24 h Hx:DCM Multi-layer silica column LRMS [52]
intestine AgNO3 silica column
2010 Losada S. Eel, conger eel, spotted Freeze- drying 2.5 g d.w. Soxhlet 24 h DCM:Hx Multi-layer silica and alumina HRMS [49]
flounder, sardine, gilthead columns;
seabream, clam, mussel
(continued on next page)
Talanta 167 (2017) 411–427
 Table 2 (continued)

Year Main/first Matrix Sample pre- Sample weight Extraction technique Extraction solvent Clean up Detection Number of Nr.
author treatment method citation*

2010 Lacorte S. Fish and milk – 5–10 g w.w. PLE DCM:Hx GPC, HRMS 6 [32]
Florisil column
2010 Blanco S.L. Fish oil – 1g – – Hx: H2SO4 digested IT 7 [74]
W.J. Pietroń, P. Małagocki

ACS
Acid silica and alumina
columns
2010 Chen M.Y.Y. Fish, seafood, – 1–150 g w.w. + Na2SO4 Hx:DCM Silica gel column HRMS 8 [40]
meat, poultry, ACS
eggs, dairy products, solvent extraction Acid silica and alumina
columns
2010 Labadie P. Eel Freeze- drying 3 g d.w. + acid silica gel Hx:DCM Centrifugation MS-MS 14 [67]
MSPD + USAL H2SO4 digestion;
2 × 20 min (130 W; centrifugation
42 Hz); Multi-layer silica column;
2010 Wang J. Honey – 20 g w.w. + Na2SO4 Acetone: DCM Dried with Na2SO4 IT/ECD 6 [59]
and wrapped with a aluminum/silica column
filter paper
ASE
2011 Zhang Z. Sheep liver Freeze- drying 0.8 g d.w. + 20 g of acid silica gel Isoheksan: DCM During extraction LRMS 13 [60]
ASE (9:1 v+v)
2011 Kalachova K. Trout, salmon, shrimps – 10 g w.w. QuECherS Ethyl acetate Mini silica column TOF 11 [72]
2011 Fontana A.R. Fish tissue, chicken breast – 1 g w.w. USAL Hx:DCM (8:2 v+v) DSPE (C18) IT 7 [68]
muscle, eggs, SPE (silica gel)
2012 Sprague M. Atlantic bluefin tuna: muscle, Freeze- drying 25–50 g w.w. ASE Izohexane ACS LRMS 0 [57]
liver, gonad, adipose tissue

414
2012 Roszko M. Milk fat – 5 g l.w. Lipid gravity separation Hx GPC IT [76]
+ Na2SO4 Multi-layer silica column
SPM (semi-permeable with AgNO3
membrane)
2012 Waszak I. Flounder Freeze- drying 10 g d.w. ASE DCM:Hx Multi-layer silica column ECD [61]
2012 Mackintosh S.A. Lake trout, yellow perch, round – 4 g w.w. + Na2SO4 DCM:Hx GPC HRMS [89]
gobies ASE Acid silica column MS-MS
2013 Jürgens M. D. Fish: Roach, Bleak, Eel – 5 g w.w + Na2SO4 DCM Acid silica column LRMS [53]
Soxhlet overnight GPC
2013 Kalachova K. Fish – 10 g w.w. QuECherS Ethyl acetate Mini silica column MS-MS [71]
2013 Zacs D. Wild salmon Freeze- drying - Soxhlet 16 h DCM:Hx GPC, acid silica and frolisil HRMS [54]
columns
Carbon: celite (1:1)
digested by 37N H2SO4
layers separations by
centrifugation
2013 Sühring R. Eel Mixed with 1 g f.w. + Na2SO4 DCM GPC, LRMS [87]
Na2SO4 ASE 10% deactivated
silica gel
2014 Baron E. Fish, dolphin blubber, bird eggs Freeze- drying 1 g d.w. alumina DCM:Hx H2SO4 digestion MS-MS [63]
PLE SPE alumina (AL-N, 5 g)
2014 Poma G. Zebra mussels, fish Freeze- drying 0.1–1 g d.w. Soxhlet Hx: Acetone GPC IT [46]
(3:1 v+v) Multi-layer silica/Florisil
column
2015 Sapozhnikova Y. Croaker, Salmon – 4 g w.w. QuECherS MeCN During extraction, filtered MS-MS [69]
2015 Couderc M. Eel Freeze- drying 1 g d.w. ASE Toluene: Acid silica, Florisil, HRMS [64]
acetone (7:3, v+v) celite/carbon columns.
2015 Portolés, T Fish, prawn, squid – 6–200 g w.w. MSPD Acetone/Hx Multi-layer silica MS-MS [70]
+silica gel/Na2SO4 Carbon
(continued on next page)
Talanta 167 (2017) 411–427
W.J. Pietroń, P. Małagocki Talanta 167 (2017) 411–427

[65]

[45]

[66]

[55]
[88]

[83]
Nr. The exception are the methods based on dispersive SPE sample
preparation where water is added to samples before extraction [46].
Freeze-dried samples are usually stored in the refrigerator or at room
Number of

temperature protected against sunlight.

citation*

2.1. Extraction techniques

Selective and exhaustive extraction is the basis of success of any

analytical method and directly influences the quality of the results.
Detection

PBDEs lipid affinity requires non-polar to medium polarity extraction

method

MS-MS
HRMS

LRMS

LRMS

LRMS
LRMS
solvents. Due to the wide range of molecular masses (250–960 units)
and differences in physical properties, classical extraction may not be
sufficient for all PBDE congeners [47]. For this reason, careful
Florisil/ acid silica gel columns
Florisil/ acid silica gel columns

optimization of the extraction process is required. Organic solvent

tandem SPE (acid silica and

polarity and density, extraction time, temperature, pressure, stability of

H2SO4 (98%) digestion

Acid silica gel/Florisil

analytes and cost-efficiency should be taken into account. The subject

D-SPE (acid silica)

acid silica column

was recently extensively reviewed by Berton et al. [48] and we briefly

summarize it here.
Clean up

Solvents commonly used for PBDEs extraction from food of animal

alumina)

origin are n-hexane, dichloromethane, acetone, ethyl acetate, acetoni-

ACS

trile or their mixtures (Table 2). In the reviewed studies researchers

optimized the following extraction techniques:
Solvent extraction – does not require expensive or sophisticated
MeCN:toluene (9:1, v+v)
Isopropanol:diethylether

Hx: acetone (8:2, v+v)

Hx: acetone (1:1, v+v)

instrumentation, so it is relatively cheap, but also inefficient. Several

Hx:diethylether (9:1)
Extraction solvent

repetitions of the extraction step often make it time-consuming, and

Toluene/acetone
(2.5: 1 v+v) and

demanding in terms of reagents amounts, thus raising the cost of the

(70:30, v+v)

procedure [49–55].
DCM:Hx

Soxhlet extraction – the most classic extraction in the POPs analysis

being characterized by high efficiency, but demanding in terms of time
and solvents amounts. Expensive equipment is not required
Extraction technique

[12,34,53,56–65].
Pressurized Liquid Extraction (PLE) – analytes elution from the
ACS – automatic clean up system; C* – according to Web of Knowledge; + – indicates addition to sample or extraction cell.

matrix is performed under elevated pressure (100−120 bar) and

temperature (80–130 °C). The apparatus allows for an efficient and
quick extraction, applying 2 or 3 extraction cycles in less than 30 min,
Soxhlet
USAL

without operator intervention. However, the relatively high cost of

ASE

ASE

PLE
LLE

apparatus maintenance and use should be taken into account [39,66–

76].
0.2, 1 or 2 g d.w.
Sample weight

Ultrasound-Assisted Leaching (USAL) –the mass transfer of ana-

( < 20%, 2–20

lytes to extraction solvent is improved by ultrasonic radiation causing

or < 2 fat)
40 g w.w.

10 g w.w.

cavitation and mechanical mixing. The thermal decay of heat-sensitive

1 g d.w.

compounds is avoided since it is a non-thermal process [77,78].

Microwave-Assisted Extraction (MAE) – solvent extraction accel-
–

erated by microwave energy sample heating. It is characterized by low

Freeze- drying

Freeze- drying
Freeze- drying

Freeze- drying
Sample pre-

solvent demand and implementation simplicity. Not often used due to

treatment

the unknown impact of microwaves on analytes and the necessity to

apply polar extraction solvents. Moreover, obtained extracts require an
additional cleanup step (e.g. filtration)[54].
–

Matrix Solid Phase Dispersion (MSPD) – is a modification of solid

Crustacean and mollusks, milk,
fish, eggs, ovine liver, muscle

phase extraction (SPE). After liquid-liquid extraction the sorbent and

Fish, meat, oil, eggs, milk

drying agent, both in the form of powder, are added to the organic
Chicken and goose eggs

phase. Interfering substances, such as fats or pigments, are adsorbed

on the sorbent and the upper organic layer is concentrated. Although
Meat, eggs, milk,

fish oil, mussels

this method is dedicated to the analysis of pesticides and plant samples

Human Milk

Cheese, fish,

with a high water content, its popularity in the analysis of POPs is

Matrix

Mussel

rising [46,77,79–82].
To summarize, the most popular extraction techniques of PBDEs
were: Soxhlet, PLE, solvent extraction, and eventually assisted with
microwave energy (MAE) or ultrasounds (USAL). Increasing numbers
of methods extracting and purifying extracts in one step can be found
Martellini T.
Main/first

Zeng Y.-H.
Table 2 (continued)

Bichon E.

in the literature. Acidic silica gel was added to the bottom of PLE
Poma G.
author

Dosis I.
Lin Y.

extraction cells to facilitate the lipid oxidation; nevertheless, the

extracts required an additional cleanup [56,58,70,77,82]. Losada and
coworkers compared three types of potential lipid retainers (silica gel,
Year

2016

2016

2016

2016
2016

2016

Florisil and alumina) and optimized the direct purification for 0.5 g of
lyophilized salmon during ASE. The cleanest extracts and recoveries of

415
W.J. Pietroń, P. Małagocki Talanta 167 (2017) 411–427

Table 3
Comparison of chromatography columns dimensions for PBDEs and detection ability with ECD, ECNI MS and EI MS detection.

Column type DB-1 DB-5 HT-5 DB-17 DB-XLB HT-8 CP-Sil19

Dimension(m×mm×µm) 30×0.25×0.25 30×0.25×0.25 30×0.25×0.10 30×0.25×0.25 30×0.25×0.25 25×0.22×0.25 17×0.15×0.30

ECD and ECNI +++ +++ + + +++++ ++++ ++
MS +++ +++ + ++ +++ +++ ++
Congener coelution (with the 28 (16,33) 28 (16,33) 28 (16,33,38) 49 (62) 49 (46,48,71,68) 28 (16,33,38) 28 (16,33,38)
same m/z) 49 (68,80) 49 (68) 49 (68) 99 (155) 49 (51,75)
49 (68) 99 (114)
183 (MeTBBP-A, 183 (MeTBBP-A, 100 (116) 100 (127) 49 (68) 183 138 (109,120) 153 (166)
BB153) BB153) (PBB153)
138 (109) 154 (168) 153 (HBCD) 183 (126) 183 (PBB153)
154 (HBCD) 183 (105)

between 83% and 108% were obtained using Florisil and n-hexane:di- determination due to their physical-chemical properties. Liquid chro-
chloromethane 9:1 (v/v) [66]. Labandeira et al. and Baron et al. applied matography was used less frequently and only in connection with mass
alumina directly in PLE cell, obtaining PBDEs recoveries in the range spectrometry [88,89].
52−103% [72,73].
Modern techniques such as MSPD or dispersive SPE were also
applied to PBDEs extraction [46,77,79–82]. Kalachova et al. replaced 3.1. GC columns
acetonitrile with ethyl acetate which is more efficient at penetrating
water containing matrices such as fish/shrimps thus enabling the Proper column selection determines the selectivity of the analytical
effective isolation of non-polar analytes [46]. method. PBDEs are compounds of low polarity, therefore the majority of
selected GC columns contain dimethylpolysiloxane with modification from
1% to 50% phenyl. The highest resolution, stability and response for PBDEs
2.2. Clean up procedures
were achieved when analytical columns with 1–5% phenyl additive were
applied [90]. The comparison of 126 PBDE congeners elution using
The separation of PBDEs from interfering compounds requires highly
different stationary phases was presented by Korytar and coworkers.
selective sample treatment. The elimination of lipids extracted together
Tests were performed on five capillary columns (30 m×0.25 mm) using a
with PBDE is necessary. Direct digestion with sulfuric acid [28,54,55,73]
gas chromatograph equipped with ECD. The DB-XLB column was found to
and saponification with 1 M KOH followed by liquid-liquid extraction [49]
be the most efficient for BDE congener-specific separation (56 BDEs co-
were applied. Commonly, the elimination of lipids is based on liquid
elutions), with the DB-1 column as runner-up (62 co-elutions). The latter
chromatography (LC) using sulfuric acid-modified silica gel columns, where
one is preferred for routine analysis due to the lower degradation of hepta-
fats are oxidized [12,34,49,50,54,55,57,63–65,69,74,75,82–84]. Potassium
and higher brominated congeners [91]. The best separation for ten PBDE
hydroxide impregnated silica gel decomposes other interfering contami-
congeners in food (118/2014/EU) was achieved on DB-1, DB-5 and DB-
nants and it is frequently employed in multi-layer columns containing
XLB columns (Table 3). Co-elutions with other PBDEs were only observed
acidic, neutral and alkaline silica gel [51,56,59,61,62,68,71,77,85]. Another
for BDE-28 and 49; however, mass spectrometry is required for the
lipid elimination method is size exclusion chromatography (SEC), also
determination of BDE-153 and 183, to be resolved from other brominated
known as gel permeation chromatography (GPC) when an organic solvent
compounds such as hexabromocyclododecanes (HBCDDs), PBBs, tetra-
is used as the mobile phase [49,64,85,86]. GPC is a solvent devourer and
bromobisphenol-A (TBBP-A) or TBBPA dimethyl ether (MeTBBP-A). The
frequently subsequent oxidation of remaining lipids is necessary
30 m DB-XLB or DB-17 columns should be used to obtain the separation of
[12,56,60,63,64,85].
BDE-28 from 16 and 33 congeners. The biggest challenge remains the
PBDEs separation from other POPs, such as PCDD/Fs or PBDD/Fs,
separation of BDE-49 from other tetra-BDEs, since co-elution was observed
is often achieved by solid phase extraction (SPE), using alumina
for all columns compared [91]. The 50 m column is required to separate
[28,34,50,57,59,69,73,75,82,83]. PBDEs are applied in the n-hexane
BDE-153 and TBBP-A, but this is accompanied by the degradation of octa-
and eluted with dichloromethane [83] or with mixtures of n-hexane
and higher PBDE congeners [12].
and dichloromethane (20% to 50% of dichloromethane) [50,51,59,60,
Retention time is proportional to compound molecular mass, and
67,69,75,77,87]. The separation was also performed using Florisil, with
long residence time at high temperatures may lead to thermal
n-hexane used as PBDEs eluent [39,56,64,65,74]. The PBDEs separa-
degradation of the highly brominated PBDEs. The 30 m column was
tion from other halogen compounds such as: PBBs, PCBs, PCDD/Fs
used in the United States Environmental Protection Agency reference
and PBDD/F, is necessary for e.g. electron capture detector (ECD). It
method (US EPA 1614) and by Huwe et al. [45,84]. Increasing the flow
can be accomplished using silica gel modified with 10% AgNO3
of carrier gas allowed the elution of BDE-209 within 45 min. BDE-209
[58,62,85]. Carbon or carbon:celite column were also included in the
separation using columns longer than 30 m seems to be impossible
purification step [51,64,74]. The automatic cleanup system (ACS)
[51,54,56,86,87]. Some authors use two columns: a shorter one
comprising acidic silica, multi-layer silica, alumina and carbon col-
(5–15 m) for unstable congeners determination, and a longer one
umns was applied for PBDE determination [50,52,67,76,83,84,87].
(30–60 m) for optimal separation of other PBDEs [12,39,60,62,
The separation of PBDEs from PCDD/F or PBDD/F was realized by an
65,72,76,92]. Both steep temperature gradient and fast mobile phase
in-line combination of alumina and carbon columns. Nevertheless,
flow (3 ml/min) reduce BDE-209 degradation [53,60,92].
efficient PBDEs and PCBs separation using ACS was not achieved [87].
Separation using a 15 m analytical column was unsatisfactory,
Lin et al. elaborated a tandem SPE method based on acid silica and
which is in line with Korytar et al. [91]. Co-eluting chromatographic
alumina, obtaining 12.5-times lower solvent consumption (40 ml) and
pairs BDE-17 and 25, 28 and 33 [49], 49 and 71 [83], 197 and 204
2-times lower blank levels when compared to ACS [75].
were observed [44]. Moreover, the simultaneous co-elution of BDE-
198, 199, 200 and 203 was also reported [77]. It should be emphasized
3. Chromatography that for ECD and NCI-MS co-elution of different PBDE congeners and
other BFRs may lead to overestimated results (Table 3). According to
Gas chromatography (GC) is the technique of choice for PBDEs Table 3 and due to EC recommendation the major issue is the co-

416
W.J. Pietroń, P. Małagocki Talanta 167 (2017) 411–427

Table 4
Details of GC-ECD techniques.

Main/ Year Congeners Injection Column Detector LOD LOQ

First temperature
author Type Volume Temperature Type Dimensions [°C] [pg/g] [pg/
[°C] (manufacture) g]

Johnson- 2005 183, 203, 209 Splitless 2 µL 250 ZB-5 5 m×0.25 mm×0.25 µm 280 1–3 l.w. – [51]
Restre- (Phenomenex) BDE-
po 209:
22 l.w.
Gómara B. 2006 183, 184, 191, Splitless – 300 DB-5 (J & W) 15 m×0.2 mm×0.2 µm 300 0.01–0.55 [73]
196, 197, 209 w.w.
0.03–
0.4 l.w.
BDE-
209:
1,84 l.w.
Tapie N. 2008 47, 99, 119, – – – HP-5 ms 60 m×0.25 mm×0.25 µm 300 1100–2600 3600 – [44]
153, 190 (Agilent) d.w. 8600 d.
w.
Wang D. 2008 196, 197, 207, Splitless 2.2 µL 300 DB-5 (J & W) 15 m×0.25 mm×0.25 µm 330 10–50 l.w. – [58]
206, 209 BDE-
209:
50 l.w.
Wang J. 2010 196, 197, 207, Splitless 2 µL 300 DB-5MS 15 m×0.25 mm×0.25 µm – 5–14 w.w. [59]
206, 209 BDE-
209:
30 w.w.
Waszak I. 2012 28, 47, 99, – – – – 60 m×0.25 mm×0.1 µm – 370– – [61]
100, 153, 154, 440 l.w.
183 2–9 w.w.

l.w. – lipid weight; d.w. – dry weight; w.w. –wet weight.

elution of BDE-28 and BDE-49 with other congeners. Recently, Bichon
et al. compared six columns with a common film thickness (0.1 µm):
two short (15 m) “Optima 5 HT” columns of different internal
diameters (0.25 mm and 0.32 mm) and four very short “Optima 5”
columns (10 m, 5 m, 2.5 m and 1.25 m). The comparison was made at
the same carrier gas velocity (50 cm s−1) and the 2.5 m column was
selected as the best one [92].
3.2. Injection
time in the injector is much shorter than elution, so column tempera-
ture is the more important factor.
4. Detection
According to the EC recommendation, PBDEs determination in
food requires a limit of detection (LOD) below 10 ppt. Obvious choices
for researchers dealing with PBDE determination in food are types of
chromatography and ionization modes.

Split/splitless, programmable temperature vaporization (PTV) and 4.1. LC-MS

on-column injection are preferable techniques used in PBDEs analysis.
The influence of injection types and its impact on the final result was
extensively investigated by Stapleton [90]. Briefly, the most popular is
splitless injection ensuring high sensitivity with some limitations.
Excessive temperature or long analyte residence time in the injector
may cause decomposition of high molecular mass PBDEs, especially
BDE-209 with a melting point assessment of between 300 and 310 °C
and a decomposition temperature above 320 °C [93]. Adverse tem-
perature impact can be limited by proper control of the gas flow in the
injector, or the use of a special injection mode, e.g. “pressure pulse”
[83,92]. Precise optimization of the PTV injector e.g. faster sample
transfer leads to shorter analyte contact time with the liner surface and
reduces the impact of high temperatures. The temperature disadvan-
tage is not present in cool on-column injection, when the sample enters
the chromatography column through a special pre-column without a
stationary phase. This type of injection requires very clean extracts and
the injected volume is limited (usually below 1 µL). In addition, faster
degradation of the chromatography column accelerated by impurities
was observed. The pulsed split injection (1:5 split ratio) was also
investigated. Symmetric peak shapes and better separation between
congeners were obtained; however, with decreased sensitivity [92].
Moreover the system cleanliness ought to be of a particular interest
because active sites on dirty injector liners could increase high
molecular mass PBDEs decomposition [90,92]. Anyway, residence
Liquid chromatography combined with mass spectrometry (LC-MS)
is not a common analytical technique used for PBDEs determination.
Two ionization methods were applied for PBDEs determination by
liquid chromatography combined with mass spectrometry:
Atmospheric Pressure Chemical Ionization (APCI) and Atmospheric
Pressure Photo Ionization (APPI) [88,89]. APCI in the positive mode
led to the formation of [M]+• ions; however, the process has a very low
level of efficiency. The elevated KOW values (up to 6) and the absence of
labile protons for the whole homologue group makes APCI unsuitable
for PBDEs determination. Similar results were described for negative
APCI where [M-H]- ions are formed; moreover, the absence of
hydrogen atoms in the BDE-209 molecule excludes this ionization
method. Reported results suggest APPI is more efficient than APCI in
PBDE analysis. The achieved APPI limits of detection were in the
ranges of 200–400 pg and 500–1500 pg injected respectively for di- to
pentaBDE and hexa- to decaBDE [88].
4.2. GC-ECD
GC coupled with electron capture detection is characterized by a
low limit of detection for halogenated compounds. Despite low
selectivity and the need of confirmation, ECD is used to determine
the PBDEs concentrations in food of animal origin (Table 2) and

417
 Table 5
Details of GC-LRMS techniques.

Main/First Year Congeners Injection Column Ionization LOD LOQ

author method
Type Volume Temperature [°C] Type Dimensions (reagent gas) [pg/g] [pg/g]
(manufacturer)
W.J. Pietroń, P. Małagocki

Huwe J. 2002 8, 15, 47, 85, 99, 100, 119, 153, 154, On- – – DB−5 ms 30 m EI – 10–470 l.w. [75]
155, 183 column (J & W)
209 870 l.w.
Jacobs, M. N. 2002 28, 47, 66, 71, 75, 99, 100, 153, 154 PTV 1 µL 90- > 290 AT−5 10 m×0.1 mm×0.1 µm (narrow EI 100−400 l.w. – [47]
solvent (Alltech) bore)
vent
de Boer J. 2003 47, 85, 99, 138, 153 PTV – 50- > 75 CP Sil 8 50 m×0.25 mm×0.25 µm ECNI – 20−800 d.w. [10]
209 Pulse- – 275 CP Sil 8 15 m×0.25 mm×0.25 µm (methane) – 30−21,000
pressure d.w.
Voorspoels S. 2003 28, 47, 99, 100, 153, 154, 183 PTV 1 µL 90- > 290 HT−8 10 m×0.1 mm×0.1 µm (narrow ECNI – 10–80 pg/g [43]
bore) w.w.
(SGE) 25 m×0.22 mm×0.25 µm if lipid (methane)
present
209 1 µL 90−305 AT−5 (Alltech) 15 m×0.18 mm x 0. 1 µm 2800–3500
w.w.
Labandeira A. 2006 1, 2, 3, 7, 8, 10, 11, 12, 13, 15, 17, 25, Splitless 2 µL 275 HP−5 30 m×0.25 mm NCI 77−736 l.w. – [62]
28, 30, 32, 33, 35, 37, 47, 49, 66, 71, 75, (ammonia)
77, 85, 99, 100, 116, 118, 119, 126, 138,
153, 154, 155, 166, 181, 183, 190
209 (only in sediments) DB−5 ms 15 m×0.25 mm×0.25 µm
Luo Q. 2007 209 Splitless 1 µL 250−280 DB−5 ms 15 m×0.25 mm×0.1 µm EI 1000 w.w. [27]

418
–
(J & W) (70 eV)
Pulkrabová J. 2007 28, 37, 47, 49, 66, 85, 99, 100, 153, 154, Splitless 1 µL 275 DB-XLB 30 m×0.25 mm x 0.1 µm NCI 15–20 l.w. 3×LOD [50]
183 (J & W) (methane)
209 285 15 m×0.25 mm x 0.1 µm 2000 l.w. 3×LOD
Akutsu K. 2008 28, 25, 28, 30, 32, 35, 37, 47, 49, 66, Splitless 1 µL 250 DB−1MS(Agilent) 15 m×0.25 mm×0.25 µm EI 10 w.w. – [39]
71, 75, 77, 85, 99, 100, 116, 118, 119, 50–100
126, 138, 153,154, 155, 166, 181, w.w.
183, 190, 196, 197, 203,
206, 207, 208, 209
Shaw S.D. 2008 3, 15, 17, 25, 28, 30, 35, 37, 47, 49, 71, – – – BD-XLB (J & W) 30 m×0.25 mm×0.25 µm – 50−860 w.w. – [42]
75, 77, 85, 99, 100, 116, 118, 119, 126,
153, 154, 155
Li Y.F. 2010 28, 47, 99, 100, 153, Splitless 1 µL 265 DB−5MS 30 m×0.25 mm×0.25 µm EI – 5–30 l.w. [52]
154, 183,
209 15 m×0.25 mm×0.25 µm NCI – 40 l.w.
(methane)
Zhang Z. 2011 28, 47, 99, 100, 153, 154, 183 Splitless 3 µL 250 ZB−5 ms 30 m×0.25 mm×0.25 µm EI 5–96 d.w. 16−319 d.w. [60]
(Phenomenex)
Sprague M. 2012 28, 47, 49, 66, 99,119, 100, 153, 154, Splitless 1 µL 225 ZB5-ms (Phenomenex) 30 m×0.25 mm×0.25 µm NCI 6–21 w.w. 18−63 w.w. [57]
183 (methane)
Jürgens M. D. 2013 28, 47, 99, 100, 153, 154 Splitless – – DB−5 30 m×0.25 mm×0.1 µm EI 5–31 w.w. – [53]
(J & W)
Sühring R. 2013 47, 66, 99, 100, 153, 154, 183 – – – HP−5MS 30 m×0.25 mm×0.25 µm NCI 51–140 w.w. 170–460 w.w. [87]
(J & W) (methane) 200–530 l.w. 660–
1800 l.w.
Dosis I. 2016 17, 28, 47, 66, 71, 85, 99, 100, 153, 154, SPI 1 µL 85- > 300 DB−5 HT 15 m×0.25 mm×0.1 µm ECNI 0.1−10 l.w. – [45]
183, 190, 209 (J & W) (methane)
(continued on next page)
Talanta 167 (2017) 411–427
W.J. Pietroń, P. Małagocki Talanta 167 (2017) 411–427

reported LODs were in the range of 0.03−440 pg/g lipid weight (l.w.),

[66]

[55]

[88]
0.01−30 pg/g wet weight (w.w.) and 1100−2600 pg/g dry weight (d.w.)
(Table 4). GC-ECD may serve as an alternative to GC-MS, since the
latter usually gives unsatisfactory results for high molecular mass

100 w.w.
[pg/g]

compounds [56,61,68]. GC-ECD was successfully applied by Gómara

5 w.w.
LOQ

et al. for analysis of hepta- to deca-BDE congeners in a wide range of

–

–
food matrices, with LODs at very low levels 0.01−0.55 pg/g w.w. and
0.03−1.84 pg/g l.w. [56]. ECD was also adopted to detect the BDE-183,
0,9−7,5 pg/

and heavier congeners in fish, dolphin tissue and fish oil [61,68]. ECD's
400 l.w.
[pg/g]

MDLs
LOD

200–
lack of molecular mass specificity allows simultaneous observation of
µL

– analytes and its degradation products. This enables monitoring of

BDE-209 degradation in honey achieving LODs at 5−30 pg/g w.w. for
(reagent gas)

degradation products (BDE-196, 197, 206, 207) [69]. Taking into

Ionization

account sensitivity and relatively low cost of equipment purchase and

(methane)
method

maintenance, ECD is sometimes used in PBDEs determination in food

ECNI

ECNI
NCI

of animal origin [54,71]. Nevertheless, lack of selectivity for other

compounds containing highly electronegative atoms, like other POPs or
l.w. – lipid weight; d.w. – dry weight; w.w. –wet weight, SPI - septum-equipped temperature-programmable injector, MDLs – method detection limits, bold –13C labeled standard

BFRs, may result in their overestimation. ECD is not a real alternative

to mass spectrometers in case of trace PBDEs determination in food
and obtained results should be confirmed.
30 m×0.25 mm×0.25 µm

15 m×0.25 mm×0.25 µm
30 m×0.25 mm×0.25 µm
15 m×0.25 mm×0.1 µm

15 m×0.25 mm×0.1 µm

4.3. GC-MS
Dimensions

Mass spectrometry (MS) provides both quantification and identifi-

cation by mass to ion charge ratio. Available mass spectrometers offer a
wide spectrum of accuracy, their sensitivity depending both on the type
of instrument and ionization parameters. In the case of PBDEs, the
most common ionization techniques are electron ionization (EI),
negative chemical ionization (NCI) and electron capture negative
(manufacturer)

ionization (ECNI). In EI with a 35 eV ion source electron energy, the

molecular ions [M]+•were the most abundant for congeners with five or
Column

DB-5HT
DB-XLB

less bromine atoms and [M-2Br]+• ions for the remaining congeners
(J & W)
Type

HP-5

DB-5

[94]. For the 70 eV variant the most abundant ions are [M-2Br]+•,
[M]+• and [M-2Br]2+•. The general tendency is that highly brominated
Temperature [°C]

congeners are vulnerable to the loss of bromine atoms upon EI.

90- > 295 (25 min)-

Moreover, ortho bromine substitution influences mass spectrum and

> 310 (5 min)

ion abundance [95].

In both NCI and ECNI the [Br]- of m/z=79 and 81 or [HBr2]- of m/
z=161 ions were monitored as the most abundant ones
[12,53,55,60,62,72]. Moreover, it is also possible to monitor [M-
–

HBr]-, [M-HBr2]-, [M-HBr3]- or [M-HBr4]- ions but their abundances

Volume

are much lower compared with Br– and [HBr2]– except the congeners
1 µL

with bromine substitution in all four ortho positions [94–96]. Methane

–

was the most popular reagent gas [60,62,97], but ammonia was also
Injection

applied for NCI [72]. In the ECNI, methane was used as a moderating
Type

gas [55,98]. NCI and ECNI have a 15 times higher sensitivity than EI
PTV
–

for molecules with higher bromine content. However, low selectivity

together with the co-elution of PBDE congeners (e.g. BDE-126 and
183, 196, 197, 203, 206, 207, 208, 209

28, 49, 47, 99, 100, 153, 154, 138, 183

119, 99, 85, 126, 154, 153, 138, 156,

28, 47, 66, 85, 99, 100, 138, 153, 154

7, 15, 17, 28, 49, 71, 47, 66, 77, 100,

155) hinders their determination by these systems and makes them

unsuitable for the identification of PBDE congeners proposed in the EC
recommendation [44,94].
Recently, the potential of APCI used with the GC-MS/MS triple
quadrupole system has been explored for sensitive determination of
BFRs [80]. The “soft” ionization promotes the formation of [M]+• by
charge transfer mechanism and [M+H]+• ions by proton transfer
184, 183, 191
Congeners

mechanism from water vapor traces. Those ions were commonly base
peaks of the spectrum, with poor fragmentation compared to the high
209

209

degree of fragmentation generally observed under EI. These ion

formation mechanisms were observed even under “dry” conditions
Year

2016

2016

2016

[80] but Bichon et al. disputed this possibility [92]. In the case of tri-
and tetra-BDE the [M+H]+• intensity was higher than [M]+•, whereas
Table 5 (continued)

for pentaBDE the [M+H]+• ions are slightly more abundant, and their
Martellini T.
Main/First

intensity increases with the number of bromine substitutions.

Zeng Y.-H.

Poma G.
author

Moreover, the authors point out that the APCI ionization is not related
to PBDE bromination degree and the obtained sensitivity is better than
for previously reported ionization techniques.

419
 W.J. Pietroń, P. Małagocki

Table 6
Details of GC-HRMS techniques.

Main/First Year Congeners Injection Column LOD LOQ

author
Type Volume Temperature [°C] Type Dimensions [pg/g] [pg/g]
(manufacturer)

Alaee M. 2001 1, 2, 7, 8, 10, 12, 13, 15, 30, 32, 33, 35, 37, 47, 66, 71, 75, 77, 85, On-column 1 µL – RTX-5 (Restek) 60 m×0.25 mm×0.25 µm 95 w.w. – [77]
99, 119, 153, 190
Fernandes A. 2004 17, 28, 47, 49, 66, 71, 77, 85, 99, 100, 119, 126, 138, 153, PTV 1 µL 40- > 320- > 350 DB-5 ms (J & W) 60 m×0.25 mm 50 l.w. – [41]
154, 183
Papke O. 2004 17, 28, 47, 66, 77, 85, 99, 100, 138, 153 154, 183, 209 Splitless 1 µL 290 DB5 30 m×0.25 mm×0.1 µm 3–63 l.w. – [21]
BDE-209
78 l.w.
Johnson- 2005 28, 47, 66, 85, 99, 100, 138, 153, 154 – 2 µL 260 DB-5msITD 30 m×0.25 mm×0.25 µm 0.1–22 w.w. – [51]
Restrepo (J & W)
Liu H. 2006 17, 28, 47, 49, 66, 71, 77, 85, 99, 100, 119, 126, 138, 153, 154, Splitless 1 µL 300 HP-5 30 m×0.25 mm×0.25 µm 0–10.2 pg/g [48]
183 (Agilent)
Shaw S.D. 2008 183, 197, 209 – – – RTX-5 ms (Restek) 15 m×0.25 mm×0.1 µm – 6–400 w.w. [42]
Losada S. 2010 28, 47, 99, 100, 138, 153, 154, 183 Splitless 1 µL 280 DB-5 ms 13 m×0.18 mm×0.18 µm 0.14–15.3 w.w. 0.33–14.7 w. [49]
(J & W) w.

420
Lacorte S. 2010 7, 8/11, 13, 15, 17, 25, 28/33, 47, 49, 66, 71, 75, 77, 85, 99, Splitless 1 µL DB5 HT 17 m×0.25 mm×0.1 µm 0.7–40 d.w. [32]
100, 101, 118, 119, 126, 140, 153, 154, 155, 138/166, 181, 3.4–39 l.w.
183,
207, 206, 209 DB5 5 m×0.25 mm×0.1 µm BDE-209:
197 l.w.
Chen M.Y.Y. 2010 17, 28, 47, 49, 66, 71, 77, 85, 99, 100, 119, 126, 138, 153, 154, Splitless – 300 DB-5HT 15 m×0.25 mm×0.1 µm – RLs [40]
156, 183, 184, 191, 196, 197, 206, 207, 209(49 and 71 0.5 w.w.
coelution) > BDE-
206
1.25 w.w.
Zacs D. 2013 7, 15, 17, 28, 47, 49, 66, 71, 77, 85, 99, 100, 119, 126, 138, Splitless 1 µL 250 DB-5 ms (J & W) 30 m×0.25 mm×0.10 µm 3–10 l.w. – [54]
153, 154, 155, 166, 181, 183, 190
Couderc M. 2015 28, 47, 99, 100, 153, 154, 183 Splitless 2 µL – DB-5 ms (J & W) 30 m×0.25 mm×0.25 µm 1–5 w.w. – [64]
Lin Y. 2016 28, 47, 99, 100, 153, 154, 183209 PTV splitless 1 µL 90- > 330 DB-5HT 15 m×0.25 mm×0.1 µm 32−100 l.w. – [65]
BDE-209:
120 l.w.

TOF
Kalachova K. 2011 28, 47, 99, 100, 153, 154, 183 PTV splitless 1 µL 95- > 200- > 320 Rxi-17Sil MS 30 m×0.25 mm×0.25 µm – 500 w.w. [72]
(Restek)

13
l.w. – lipid weight; d.w. – dry weight; w.w. –wet weight, bold – C labeled standard.
Talanta 167 (2017) 411–427
W.J. Pietroń, P. Małagocki
4.3.1. GC-LRMS
The simple and cheap solution is probably the most popular mass
spectrometry technique with a quadrupole ion optic. The MS instru-
ment is small in size, has a linear mass scale, allows fast scanning and
is user-friendly, but it also allows measurement with the ultimate
attainable resolving power, so-called low resolution mass spectrometry
(LRMS). The quadrupole filters with EI, NCI and ECNI have been
successfully adapted to the quantification of PBDE in food of animal
origin (Table 5). To improve quantification, the isotopic dilution mass
spectrometry (IDMS) method was applied by some authors
[34,49,62,63,76]. Reported detection limits for mono- to octa-bromi-
nated BDE were in the ranges of 0.1–736 pg/g l.w., 5−860 pg/g w.w.
and 5−96 pg/g d.w. LOQs were in the ranges of 5−1800 pg/g l.w.,
10−3500 pg/g w.w., and 16−800 pg/g d.w. Martellni et al. reported
LODs in the range of 0.9–7.5 pg/µL, as a minimal detectable concen-
tration in the final extract [86]. Quantification of BDE-209, despite low
efficiency transportation of higher mass ions by quadrupole filters, was
also reported [34,49,55,76,84]. Akatsu et al. applied the IDMS method
in combination with low energy EI (35 eV) providing low fragmenta-
tion of the high molecular mass PBDEs, which allowed the LOD of
100 pg/g w.w. for BDE-209 to be obtained [49]. Similarly, Luo et al.
applied EI with a standard ionization energy (70 eV) to obtain LOQ for
BDE-209 at 1 ng/g w.w. [34]. Huwe et al. reported LOQ at 870 pg/g
l.w. using EI and MS resolution at 2500. According to Li et al., NCI is
more efficient than EI for the detection of high halogen content
molecules. LOQ for BDE-209 was reported at 40 pg/g l.w., but NCI
was used only for BDE-209 due to the lack of specificity for other
congeners [62]. The most sensitive technique was the LRMS-ECNI
method, with LOD for tri- to decaBDE congeners in the range of 0.01–
10 ng/g l.w. [55]. Despite low ultimate resolving power, single quadru-
pole MS can be successfully applied in routine analysis of PBDEs in
food of animal origin.
4.3.2. GC-HRMS
MS detectors which can produce a resolution higher than 4000 are
called high resolution mass spectrometry (HRMS) detectors. The
efficiency of ion transfer in an instrument with a combination of
magnetic and electric sectors is not mass dependent, so sensitivity loss
for higher mass particles is not observed. The EI with a voltage in the
range of 30−40 eV and source temperature of 250−300 °C were used to
determine the level of PBDEs (Table 6). Most researchers work with the
IDMS method using 13C12 labeled PBDEs. One of the first IDMS
methods used for PBDE determination was based on 13C12 labeled
polychlorinated diphenyl ethers (PCDE) [86]. The HRMS technique
allows the LOD value below 100 pg/g l.w. to be obtained for PBDE
congeners with nine or less bromine atoms (Table 6). The [M-2Br]+ion
used for BDE-209 allowed the LODs in the range of 78−197 pg/g l.w. to
be quantified, but the authors point out that environmental conditions
in the laboratory and purity of reagents is of major importance [58].
The lowest levels of quantification for BDE-206, 207, 209 (1.25 pg/g
w.w.) and lighter congeners (0.5 pg/g w.w.) were reported by Chen
et al. [50]. Possible interferences such as PCBs, PCDFs, polychlorinated
naphthalenes (PCNs) or polychlorinated terphenyls (PCTs) should be
taken into account when HRMS is used. Interferences from PCNs or
PCTs are solved by increasing the resolution to 10,000. If PCDFs are
present in the injected solution, chromatographic separation and even
the highest resolution may not be sufficient to rule out interferences.
However, appropriate fractionation prior to instrumental analysis
resolves this issue [96].
4.3.3. GC-TOF
Another type of high resolution mass spectrometry is time-of-flight
mass spectrometry (TOF-MS), which was also used in the field of
PBDEs analysis (Table 6). Ions are accelerated in an electric field and
subsequently pass the same distance of field-free region to reach the
detector (e.g. a photomultiplier) after a time proportional to their
421
Talanta 167 (2017) 411–427
masses. TOF was applied to determine the PBDE concentrations in fish
and shrimp samples by Kalachova et al. and reported LOQs were at
0.5 ng/g w.w. [81]. The TOF technique is sufficient for high PBDE
concentrations like the ones reported in fish [54,57,61,66]; however,
confirmation at trace levels in other types of food requires more
sensitive techniques. Furthermore, no results for congener BDE-209
were reported. Presumably, the ion reflection mirror used in the
instrument caused insufficient sensitivity or the authors’ attention
was focused mainly on the simultaneous determination of multiple
compounds (PAHs, PCBs, PBDEs). The authors point out that a
significant reduction in the LOQs may be obtained by applying the
two-dimensional gas chromatography (GC×GC) technique, but it has
not been confirmed yet for food samples. Moreover, GC-GC-TOF
technique could be considered as a future universal tool for the
simultaneous determination of multiple classes of POPs.
4.3.4. GC-MS-MS
The systems consisting of two quadrupole filters, commonly known
as tandem mass spectrometry (MS-MS) allow for the preselection of
ions in the first sector, subsequent fragmentation in the collision cell
and their separation in the other quadrupole. MS-MS is widely used in
the analysis of prohibited substances residues (e.g. drugs, hormones or
pesticides) and was also utilized in PBDEs quantification in food of
animal origin (Table 7). Labadie et al. paid special attention to the
selection and optimization of the fragmentation process in order to
obtain maximum sensitivity for 28 PBDE congeners [77]. The reported
instrumental detection limits (iLOD) were in the range of 0.05–5 pg.
The method's LOQs were in the range of 2–56 pg/g w.w. or 25–700 pg/
g l.w. for tri- to nona-BDEs and, respectively, 170 pg/g w.w. and
2110 pg/g l.w. for BDE-209. However, the authors point out that high
LOQs for some congeners (BDE-47, 99, 100, 209) are associated with
concentrations occurring in laboratory blanks. For lower brominated
congeners (tri- to pentaBDE), [M-2Br]+ ions have a higher intensity
and were selected for further fragmentation, but for real samples a high
matrix background required the use of a [M]+= > [M-2Br2]+ fragmen-
tation passage [77]. The same technique was used by Kalachova et al. in
combination with a 30 m chromatography column and allowed for the
simultaneous analysis of PBDEs, PCBs, chlorinated pesticides and
PAHs, but no data for BDE-196 and heavier congeners were presented
[81]. LOQs in fish muscle were obtained in the range of 5 −1000 pg/g
w.w., being an order of magnitude higher compared to the data by
Labadie et al. [77].
Baron et al. described the determination of PBDEs, methoxylated
PBDEs, and other flame retardants in wild birds’ eggs, dolphin tissues,
cod-liver oil and fish muscles, but the LOQs obtained do not allow for
its application to detect trace levels in food samples [73]. Sapozhnikova
et al. published a comparison of MS-MS and ELISA results for fresh
water fish and reported MS-MS LODs in the range similar to previously
mentioned papers [79]. Mackintosh et al. demonstrated an iLODs
comparison between MS-MS and HRMS systems. Surprisingly, the
results were in favor of the MS-MS system [99]. Recently, excellent
sensitivity was reached on MS-MS using APCI under charge-transfer
conditions with on-column LODs below 10 fg. However, the reported
results for BDE-209 were 10 times or higher than those obtained using
EI MS-MS. The authors explained the differences with a lack of
adequate (i.e. labeled) standard [80]. Bichon et al. compared the
APCI MS-MS system with EI HRMS obtaining an LOQ below 10 ng/
g w.w., but noted that most of the time, HRMS was still the most
repeatable method [92].
4.3.5. GC-IT
The Ion Trap (IT) captures the ions of specific m/z allowing their
subsequent multiple fragmentation (Table 8). This experiment could be
repeated and allows for multiple fragmentation passages. Impact
ionization with a standard voltage (70 eV) and the measurement of
the molecular ion or molecular and secondary ions was applied in all
 W.J. Pietroń, P. Małagocki

Table 7
Details of GC-MS-MS techniques.

Main/First Year Congeners Injection Column Ionization LOD LOQ

author method
Type Volume Temperature[°C] Type Dimensions [pg/g] [pg/g]
(manufacturer)

Labadie P. 2010 17, 28, 47, 49, 66, 71, 85, 99, 100, 119, 126, Pulsed – 285 HP-5ms (J & W) 15 m×0.25 mm×0.25 µm EI – 2–56 w.w. [67]
138, 153, 154, 156, 181, 183, 184, 191, 194, splitless 25–700 l.w.
195, 196, 201, 202, 205, 206, 207, 208, 209 BDE−209:
170 w.w.
2110 l.w.
Mackintosh S.A. 2012 1, 2, 3, 7, 10, 15, 17, 28, 30, 47, 49, 66, 71, PTV 1 µL 80- > 3 20 ZB-5ht 15 m×0.25 mm×0.1 µm EI 0.04–90 w.w. – [89]
77, 85, 99, 100, 119, 126, 138, 139, 140, Splitless (Phenomenex) BDE-209480
153, 154, 156, 169, 171, 180, 183, 184, w.w.

422
191, 196, 197, 201, 203, 204, 205, 206,
207, 208, 209
Kalachova K. 2013 28, 47, 49, 66, 85, 99, 100, 153, 154, 183 PTV 1 µL 96- > 200- > 320 Rxi-17Sil MS (Restek) 30 m×0.25 mm×0.25 µm EI – 5−1000 w.w. [71]
(unsatisfactory sensitivity for 196–209) splitless
Baron E. 2014 28, 47, 99, 100, 153, 154, 183, 209 – – 280 DB-5 ms 15 m×0.1 mm×0.1 µm EI 10–3190 l.w. 30–10600 l.w. [63]
BDE-209 BDE−209
< 10600 l.w. < 35400 l.w.
Sapozhnikova Y. 2015 28, 47, 99, 100, 153, 154 PTV 5 µL 50- > 320 Rti-5 (Restek) 15 m×0,53 mm×1 µm – 1000–2000 w. – [69]
w.
Portolés, T 2015 28, 47, 66, 85, 99, 100, 153, 154, 183, 184, Pulsed 1 µL 280 DB-1HT 15 m×0.25 mm×0.1 µm APCI 0.001–0.010 – [70]
191, 196, 197, 209 splitless (J & W) on-column
Bichon E. 2016 28, 47, 99, 100, 153, 154, 183, 209 Pulsed 1 µL 275 Optima 5 2.5 m×0.1 mm×0.1 µm APCI – 1–4 w.w. [83]
Split (1:5) (Macherey Nagel) BDE−209:
5 w.w.

l.w. – lipid weight; d.w. – dry weight; w.w. –wet weight, bold –13C labeled standard.
Talanta 167 (2017) 411–427
 W.J. Pietroń, P. Małagocki

Table 8
Details of GC-ITMS techniques.

Main/First Year Congeners Injection Column LOD LOQ

author
Type Volume Temperature[°C] Type Dimensions [pg/g] [pg/g]
(manufacturer)

Pirard C. 2003 8, 10, 11, 12, 13, 15, 17, 25, 28, 30, 32, 33, 35, 37, 47, 49, 66, 71, 75, Splitless 1 µL 140 Rtx 5ms 40 m×0.18 mm×0.20 µm 5–64 l.w. 13–123 l.w. [78]
77, 85, 99, 100, 105, 116, 119, 126, 138, 140, 153, 154, 166 (Restek)
Gómara B. 2006 17, 28, 47, 66, 85, 99, 100, 153, 154, 183, 154 Splitless 1 µL – VF-5ms (Varian) 55 m×0.25 mm×0.25 µm 0.02–4.7 w.w. – [73]
0.3–8.2 l.w.
Luo Q. 2007 3, 7, 15, 17, 28, 47, 66, 71, 77, 85, 99, 100, 119, 126, 138, 153, 154, Splitless 1 µL 250–280 DB-5ms (J & W) 30 m×0.25 mm×0.25 µm 10 w.w. – [27]
183
Wang D. 2008 3, 7, 15, 17, 28, 47, 49, 66, 71, 77, 85, 99, 100, 119, 126, 138, 153, Splitless 2.2 µL 300 DB-5ms 15 m×0.25 mm×0.25 µm 0.18–120 l.w. – [58]
154, 156, 183, 184, 191
Losada S. 2010 28, 47, 66, 85, 99, 100, 138, 153, 154 Splitless 1 µL 280 DB-5ms (J & W) 30 m×0.25 mm×0.25 µm 10–34 w.w. 34–68 w.w. [49]

423
Blanco S.L. 2010 3, 7, 15, 17, 28, 47, 49, 66, 71, 85, 99, 100, 119, 126, 138, 153, 154, Splitless 1 µL 285 DB-5HT 15 m×0.25 mm×0.1 µm 5–65 l.w. – [74]
183, 184, 191, 197, 206, 207, 209 BDE-209:
105 l.w.
Wang J. 2010 3, 7, 15, 17, 28, 47, 49, 66, 71, 77, 85, 99, 100, 119, 126, 138, 153, Splitless 1 µL 300 DB-5MS 30 m×0.25 mm×0.25 µm 0.6−10 w.w. – [59]
154, 156, 183, 184, 191
Fontana A.R. 2011 47, 99, 100, 153 Splitless 1 µL 300 VF-5ms (Varian) 25 m×0.25 mm×0.25 µm 9–44 l.w. – [68]
64–200
w.w.
Roszko M. 2012 17, 28, 47, 66, 71, 85, 99, 100, 138, 153, 154, 183, 190, 209 PTV 1 µL – DB-5ms 15 m×0.25 mm×0.25 µm 0.03–0.3 l.w. 0.1–1 l.w. [76]
(J & W) (guard column BDE-209: BDE-209:
5 m×0.53 mm) 1.2 l.w. 4 l.w.
Poma G. 2014 17, 28, 47, 66, 85, 99, 100, 153, 154, 183, 154 PTV – 70- > 280 DB-5MS (Agilent) 50 m×0.25 mm×0.25 μm 10 w.w. – [46]
14 °C/s
179, 188, 201, 202, 206, 207, 70- > 300 RXi-1MS (Restek) 12 m×0.20 mm×0.33 μm
208, 209 8 °C/s;

l.w. – lipid weight; d.w. – dry weight; w.w. –wet weight, bold –13C labeled standard.
Talanta 167 (2017) 411–427
W.J. Pietroń, P. Małagocki Talanta 167 (2017) 411–427

104 A Mean Median 10600

2000
3
10

pg/g lipid weight

703
400
197
2 132 120 105
10 50 78 53 53
25 22
1
10 10

100 1,8
1,2
4

B
10
3190
1550 1550
103 736
440
210 224 275
pg/g lipid weight

100 120
102
35 33 27 31
1 16
10 10
3
100

-1
10 0,1
0,03 0,03
-2
10
ECD LRMS HRMS IT MS-MS
Fig. 2. Comparison of LOD ranges, means and medians for (A) BDE-209 and (B) tri- to nona-BDEs.

discussed methods. IT mass spectrometry required not only instrument
optimization but also the appropriate selection of ions for further
fragmentation [56,68,83,87]. The [M−2Br]+ is selected for PBDEs with
six or more bromine atoms fragmentation and [M−2Br-COBr]+,
[M−3Br]+ or even [M−4Br]+ are reported as the most abundant
secondary ions. For lower brominated congeners, molecular ions
[M]+ or [M-2Br] + are commonly selected and the most abundant
secondary ions are [M−2Br]+ or [M−COBr]+ [83]. The lowest LODs,
equal to 0.03 pg/g l.w. and 0.02 pg/g w.w., were reported respectively
by Roszko et al. and Gómara et al. [56,60] and the highest LODs were
reported by Wang et al. −120 pg/g l.w. and Fontana et al. – 200 pg/g
w.w. [68,78]. BDE-209 was successfully determined only in two
discussed papers by applying 5 m and 15 m chromatographic columns;
the obtained LODs were between 1.2 and 105 pg/g l.w. [77,85]. The
possibility of multiple ions fragmentation, small size, easy operation as
well as low purchase and maintenance costs make IT mass spectro-
meters popular in PBDEs analysis.
4.4. Detection comparison
Detection techniques comparison is a complex task, considering the
variety of sample preparation strategies, ionization methods and finally
different results expression. Limits of detection expressed in pg/g l.w.
or ng/g l.w. are commonly reported in the literature and we selected
them to compare the discussed techniques. They fit within the range of
six orders of magnitude (Fig. 2), so arithmetic means were calculated
from minimal and maximal values of LOD ranges reported in particular
papers, and both median and averages of the means were used to
facilitate comparison. Considering the differences in properties and
consequent detection problems, the comparisons were made separately
for the group of tri- to nonaBDE and BDE-209.
For the tri- to nonaBDE group the lowest LODs in food were
obtained by ECD and IT (Fig. 2B). Also, the lowest median value equal
to 16 pg/g l.w. was calculated for the ECD technique. Slightly higher
median values were estimated for IT (31 pg/g l.w.) and HRMS (33 pg/g
l.w.). On the opposite end was the median LOD of 1550 pg/g l.w.
reported for the MS-MS technique, which is a hundredfold higher than
the medians from ECD, ITMS and HRMS and tenfold higher than
LRMS. LODs obtained using TOF-MS were 500 pg/g w.w. [46]. To
facilitate comparison we converted them according to the lipid content
reported by authors and obtained LODs of 31.3 ng/g l.w. for trout
(1.6% fat), 3.6 ng/g l.w. for salmon (14%) – and 125 ng/g l.w. for
shrimp (0.4%). The converted LODs for trout and shrimp were
significantly above the LODs reported for other techniques, but for
salmon were near MS-MS LODs. TOF MS could be a useful tool for
PBDEs detection, anyway further improvement of the technique is
required.
LODs obtained by different detection techniques for BDE-209

424
W.J. Pietroń, P. Małagocki
follow the trends for other congeners (Fig. 2A). However, high
molecular mass, thermo- and photolability make BDE-209 quantifica-
tion the most problematic issue in PBDE analysis. LODs for BDE-209
obtained using all investigated techniques are significantly higher than
for other congeners except ECD. Also, the lowest LODs were reported
for ECD with the median at 22 pg/g l.w. and the average at 25 pg/g l.w.
Slightly higher values were estimated for IT and HRMS. The least
sensitive techniques for BDE-209 detection are LRMS and MS-MS
(10,600 pg/g l.w.), therefore these techniques were not frequently
used. However, recently APCI MS-MS was involved in PBDE analysis
without sensitivity loss for highly brominated congeners. Reported
LODs were as low as 0.01 pg injected onto the column, but the lack of
many essential data values makes unit conversion and comparison with
other results impossible [80]. GC-ICP-MS (Inductively Coupled
Plasma-MS) was also introduced into PBDEs analysis obtaining
promising results, but currently it is used mainly in environmental
sample analysis [1,48,93,100].
5. Conclusion
Magnetic sector HRMS is still characterized by the highest speci-
ficity and precision in PBDE analysis. It undoubtedly fits that purpose,
and is considered to be a reference technique. High purchase and
maintenance costs are its disadvantages. The IT technique, due to its
sensitivity and low overall costs, could be an alternative to HRMS,
which has been confirmed by a large body of published research data.
ECD is the most sensitive technique; however, PCBs or other semi-
volatile halogen compounds present in food of animal origin may
interfere with PBDE congeners with up to 5 bromine atoms, necessitat-
ing results confirmation. Recent APCI implementation in GC-MS-MS
placed this technique in the top of the most sensitive ones available.
Further APCI investigation and its implementation in other detection
techniques (e.g. TOF) has the potential to increase their sensitivity.
Although PBDEs chemically constitute a homologous group, the
differences in properties hinder their determination. Detection techni-
ques producing good results in the low brominated PBDE analysis
usually fail when applied to higher brominated congeners. In addition,
the same LOQ equal to 10−11 g or lower for 10 congeners, defined in the
only international requirement for analytical methods (2014/118/EU
recommendation), is often below laboratory background levels, espe-
cially for BDE-209. Only a few methods demanding expensive and
time-consuming analysis meet these requirements. Thus trace PBDEs
determination in food is still a serious challenge for researchers.
Acknowledgments
The manuscript proofreading was funded by KNOW (Leading
National Research Centre) Scientific Consortium "Healthy Animal –
Safe Food", decision of Ministry of Science and Higher Education No.
05-1/KNOW2/2015.
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