Trends in Environmental Analytical Chemistry 17 (2018) 1–13

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Tendencias en Química Analítica Ambiental

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Dioxinas y furanos: Una revisión de las perspectivas químicas y ambientales

Asi que fi un Kanan • , fatin Samara

Universidad Americana de Sharjah, Departamento de Biología Química y Ciencias Ambientales, PO Box 26666, Sharjah, Emiratos Árabes Unidos

INFORMACIÓN DEL ARTÍCULO ABSTRACTO

palabras clave: Los contaminantes orgánicos persistentes (COP) en el medio ambiente han generado gran interés dentro de la científica fi comunidad c debido
Fuentes a su tóxico e ff ect al animal, la salud humana y el medio ambiente. Esta opinión abarca la presencia histórica de dibenzo policlorados pag- dioxins
PCDD (PCDDs) and dibenzofurans (PCDFs) in the world-wide environment. Information on exposure indicated that the main route of exposure of
PCDF
dioxins/furans to humans is through ingestion, which is discussed in this paper. In addition, we present a thorough assessment of sampling,
ambiente GC Worldwide / MS
methods for extraction, and analysis as well as the photodegradation of dioxins under various conditions. In general, extraction methods
including USEPA 8290 are the most used with high resolution gas chromatography/ high resolution mass spectrometry (HRGC/HRMS)
fotocatálisis
preferred as a detection tool. Moreover, a detailed compilation of studies of the PCDD/F concentrations and environmental sources from major
industrial regions in several countries are presented. In summary, the major sources of dioxins in the worldwide environment include
combustion and industrial sources with major challenges related to the lack of data availability in the Middle East especially with the current
Warfare con fl icts in the region.

1. Background
Persistent organic pollutants (POPs) are harmful organic compounds that are resistant to
biological, chemical, and photolytic degradation. They are persistent in the environment especially in
soils, sediments, and air for several decades [ 1 ]. Because of their toxicity and persistency, they pose
a signi fi cant threat to animal, human health, and the environment since they accumulate in the fatty
tissues of humans and animals [ 2 , 3 ]. In humans, POPs have been linked with behavioral,
reproductive, developmental, endocrine, neurologic, and immunologic adverse health e ff ects [ 4 , 5 ].
While in animals, they have caused diseases and abnormalities in a number of wildlife species
including certain kinds of birds, fi sh, and mammals. They are a global concern due to their
transportation over long distances from the point of production or release since they can evaporate
from the soils and travel through the air and condense in colder regions.
disposal of some of the PBTs and PAHs, pollution from the combustions of fossil fuels, pesticides [ 8 ].
A vital challenge is to cut back the quantity of POPs contamination and it ’ s unfolding through organic
phenomenon. The data obtained for the concentration of POPs in the food chain, is necessary to
support the implementation of policies and processes to reduce the amounts of POPs within these
chains [ 9 , 10 ]. The Stockholm treaty on POPs was instituted to control the concentration levels of
POPs within the general population, as a result, “ the dirty dozen ” was created. In speci fi c, 12 di ff tipos
Erent de COP incluyendo aldrina, clordano, dieldrina, endrina, heptacloro, hexaclorobenceno, mirex,
toxafeno, diclorodifenil tricloroetano (DDT), bifenilos policlorados, dibenzodioxinas policloradas
(PCDD) y dibenzofuranos policlorados (PCDF), se identificaron fi ed con el fin de ser eliminado y
controlado por 150 países [ 11 ].

PCDD y PCDF son generalmente clasificadas fi ed as toxic and carcinogenic unintentional

According to researchers POPs are just a subset of more dangerous materials such as
persistent, bio accumulative and toxic ((PBT)) chemicals including pesticides and organic compounds
such as γ- hexachlorocyclohexane, 1,1,1-trichloro-2,2-diethane, polychlorinated biphenyls, polycyclic
aromatic hydrocarbons (PAHs), polychlorinated naphthalene, polychlorinated dibenzo-p-dioxins
(PCDDs), poly-
chlorinated dibenzofurans (PCDFs), as well as groups of brominated
fl ame retardants such as polybrominated biphenyls (PBBs) [ 6 , 7 ]. The quantity of the POPs in the
atmosphere increases due to the massive
by-products that are present in small amounts in the environment. The major issue with PCDDs/Fs is
their extreme persistency in the environment, which is toxic to living organisms and can potentially
cause cancer. There are three main categories for dioxins and furans: polychlorinated
dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated
biphenyls (DL-PCBs). PCDDs and PCDFs are released as byproducts of anthropogenic activities, or
processes such as forest fi res [ 12 ]. They are byproducts of the synthesis or combustion of chlorine
based compounds that include some of the most toxic chemical substrates. This group of

• Corresponding author.

E-mail address: skanan@aus.edu (S. Kanan).

https://doi.org/10.1016/j.teac.2017.12.001
Received 27 September 2017; Received in revised form 6 December 2017; Accepted 14 December 2017
2214-1588/ © 2017 Elsevier B.V. All rights reserved.
S. Kanan, F. Samara
compounds include 210 possible congeners and at least seventeen have been identify as toxic with
wide ranging toxicity from which 2,3,7,8tetrachlorodibenzo-p-dioxin (TCDD), was identi fi ed as the
most toxic compound [ 1 , 13 ]. Humans are normally exposed to dioxins and furans through
contaminated food products which are often a ff ected through the accumulation of these chemicals in
the food chain and in high fat foods, such as eggs, dairy products, animal fats, and fi sh [ 11 , 14 – 19 ]. In
order to obtain the toxicity of these compounds in vivo and in vitro data involving processes such as
uptake, tissue distribution, metabolism, receptor binding, and activation was obtained in relative to the
most toxic congener 2,3,7,8-TCDD. To express concentrations of the most toxic PCDDs/Fs and
dioxin-like PCBS in relation to their toxicity toxic equivalency factors (TEFs) have been used and
determined by the comparison of its toxic or biological endpoints to those of the 2,3,7,8TCDD. TEFs
for 17 PCDD/F congeners are then used to estimate the overall dioxin-like toxic equivalency (TEQ)
found in samples, with
2,3,7,8-TCDD que tiene un TEF de referencia de la unidad. FET se utilizan como un método
consistente para informar de los efectos tóxicos de diferentes mezclas de compuestos tipo dioxina.
Han sido desarrollados para facilitar la evaluación comparativa del riesgo y el control reglamentario
de la exposición a estas mezclas [ 20 - 22 ].
El objetivo de este artículo de revisión es acceder al estado actual del análisis de
dibenzo-p-dioxinas (PCDD), dibenzofuranos policlorados (PCDF) y bifenilos policlorados similares a
las dioxinas (DLPCBs) en el entorno global utilizando algunos de los principales países como
ejemplos. Además, vamos a brie Florida y explorar y discutir las técnicas más comunes para la
extracción, limpieza y determinación instrumental de este compuestos en di ff matrices Erent, así
como las técnicas comunes para su eliminación y / o degradación. Para propósitos de simplicidad,
PCDD, PCDF y DL-PCB será a menudo referido como dioxinas en todo el papel.
2. Las fuentes comunes de PCDD, PCDF y PCB DL
Los estudios han demostrado que las concentraciones de dioxinas y furanos eran bajos en el
año 1900, y mostró signos de aumento durante los años 1920 a 1970 [ 18 , 23 ]. Esto indica que están
formados principalmente por fuentes antropogénicas, como se resume en Figura 1 . en especí fi c,
cualquier proceso que implique cloro orgánico o cloruros inorgánicos presenta una signi fi cant source
of dioxins and furans. Conical municipal waste combustion in new found land, waste incineration,
coastal pulp mill boilers burning salt laden wood, residential wood combustion, iron sintering and
electrical arc furnace steel manufacturing are the major sources of dioxins emissions as generate
80% of the total national emissions that had
2
Trends in Environmental Analytical Chemistry 17 (2018) 1–13
a total of 198 g TEQ/year according to the 1997 national inventory [ 24 ]. Steel manufacturing and iron
sintering processes were found to be among the major sources of dioxins and furans emissions
despite the fact that low levels of chloride may enter the combustion processes. In addition, extensive
studies on municipal solid waste, medical waste, sewage sludge, and hazardous waste incinerations
showed that low levels of dioxins emissions, can be achieved from even trace quantities of organic
and inorganic chlorides. An example of this common source, is the municipal solid waste in Canada,
containing seven solid waste treatment facilities having a capacity of 25 t/day and they handled 3% of
the [ 25 , 26 ].
Waste incineration is responsible for 37.6% of the total dioxin emissions from anthropogenic
sources with a 74.5 g TEQ/year [ 2 , 24 ]. Moreover, it was reported that wood can absorb signi fi cant
amounts of sodium chloride when stored in the marine waters along the west coasts of Canada.
Under certain combustion conditions, the burning of salt laden wood waste in pulp mill power boilers
leads to the formation and emission of dioxins and furans. The formation of these compounds is
favored under poor combustion conditions as the gas phase precursors formation such as
chlorophenols and polycyclic aromatic hydrocarbons will be favored [ 26 , 27 ]. Thus, dioxins and furans
can be formed through adsorption/desorption on ash particles. A total of 7.9 g TEQ/ year of dioxins
and furans emissions were resulting from coastal power boilers burning salt-laden hog fuel which is
equivalent to 4% of the total anthropogenic emissions [ 24 ]. These emissions are regulated according
to Canada wide-standards to be reduced, in 2006, to 0.5 ng TEQ/m 3 for existing reboilers and 0.1 ng
TEQ/m 3 for new reboilers [ 28 ]. Other main sources around the world will be discussed in section
3 of this paper.
Finally, dioxins are also formed in pulp and paper mills e ffl uent discharge as a result chlorine
bleaching. Since the emissions of dioxins and furans from pulp and paper mills is under the legal limit
of quanti fi cations, a total emission of 2 g TEQ/year has resulted from all pulp and paper mills in
Canada [ 24 ]. Their presence could be detected in air, water, and soil. It is shown that 90% of human
exposure to dioxins is attributed to food consumption, hence, creating various adverse health e ff ects
in human and animals. Dioxins vary in their toxicity that depends mainly on the type of dioxin,
frequency and duration of the exposure [ 3 , 24 , 29 , 30 ]. Pentachlorophenol (from the textile industry) has
been suggested as the major source of PCDD/F in sewage sludge. For this reason, countries such as
Germany, banned the use of the chemical resulting in a signi fi cant reduction of PCDD/F levels in
sewage sludge [ 31 ].
Fig. 1. Major Dioxins Sources in the Environment.
S. Kanan, F. Samara
3. Most common methods for analysis and detection
3.1. Extraction and clean-up techniques
Various extraction and determination methods of dioxins and dioxin- like compounds from di ff erent
matrices have been reported [ 32 – 35 ]. Por ejemplo, Suzuki et al. sugerido el uso de extracción por
solvente para muestras de suelo y polvo con sólidos grandes, tales como piedras y ramitas, que
deben ser eliminados manualmente. A continuación, las muestras de suelo se colocan en un tamiz y
se agitaron para eliminar la materia particulada grande luego se mezcla con una mezcla 1: 1 de
acetona y hexadecano con ser la mezcla resultante fi se filtra y se almacena en un almacenamiento en
frío hasta que se haga el análisis [ 33 ]. Por el contrario, para la extracción de dioxinas a partir de
muestras de aire, Li et al. sugerido pasar la muestra a través de una mezcla 1: 1 de hexadecano y
diclorometano. Con el fin de eliminar cualquier materia particulada no disuelta, la solución resultante
se pasó a través de una columna de gel de sílice de múltiples capas y luego a través de una columna
de carbón activado. Las dioxinas adsorbidas a continuación se pueden eluir usando mezcla de
diclorometano-hexadecano con todas las muestras se almacenan en frío antes de su análisis [ 34 ]. En
las muestras de agua, Gao et al. propuesto fi ltrado y pasando las muestras de agua a través de una
columna que contiene una resina hidrófoba, tales como XAD-2, que las trampas dioxinas disuelven.
Después del secado, una solución 1: 1 de diclorometano y hexadecano eluye las dioxinas con el fi solución de contaminantes de la cadena alimentaria de la Autoridad Europea de Seguridad Alimentaria (Panel
final se recoge y se almacena en la temperatura fría antes del análisis [ 35 ]. In the case of sludge
samples, sludge extracts are transferred to hexane and acidtreated with concentrated sulfuric acid.
Furthermore, after evaporation, extracts are scrubbed in a multi-layered silica gel column, followed by
a basic alumina column, and fi nally through a PX-21 active carbon column [ 36 , 37 ].
Analysis of dioxins contaminated in soil is very critical, hence, advanced soil mineralogy methods
have to be used in this process. In speci fi c, the extraction of the dioxins can be done through various
methods such as pressurized liquid extraction strategy with sulfuric acid-impregnated silica is used for
the extractions of the compounds [ 38 ]. The absorbance arising is inversely proportional to the amount
of dioxins, from which success from this technique becomes operational [ 39 ]. Este método requiere el
cálculo de la equivalencia de toxicidad de la prueba por las disposiciones de la protección del medio
ambiente informe de la agencia de los Estados Unidos [ 40 ]. técnica de extracción rápida tiene una
extracción de correo FFI eficiencia de aproximadamente 81%. Esto da automáticamente una
indicación de que es posible extraer dioxinas tras la posibilidad de omitir el paso de secado por aire [ 12
, 41 - 43 ].
Existen otros métodos descritos para los tejidos de plasma sanguíneo y animales donde la
extracción y la limpieza se realiza en varias etapas que incluyen una extracción inicial con un
cartucho de sílice C18 unido, seguido por limpieza con un doble cartucho compuesto de cartucho de
ácido bencenosulfónico unido en serie con un cartucho de sílice, y una fi paso final que incorpora una Floridafuranos (HDD / HDF) a 50.000 - 100.000 de un poder de resolución en el tiempo de cromatografía de
cartucho orisil [ 44 ]. Por otra parte, otros estudios han informado de análisis de la leche usando la
Soxhlet a extraer y luego limpiaron usando el sistema Power-Prep de forma automática y / o el uso
de cromatografía de permeación en gel, alúmina limpieza y cromatografía de carbón grafitado porosa
[ 45 , 46 ]. En general, basado en la matriz de la extracción y limpieza de los procedimientos puede
variar.
3.2. cuanti fi técnicas de cationes y detección
Tradicionalmente, los niveles de toxicidad de PCDD / Fs se han determinado por espectrometría
de cromatografía de gases / masas de alta resolución (HRGC / HRMS) Análisis para concentraciones
de congéneres y reportado como EQT. El EQT total de una mezcla es la suma de la TEF de cada
individuo veces congéneres su concentración. Algunos parámetros comunes para el análisis de GC /
MS incluyen la temperatura de inyección a 300 ° C con la temperatura de la columna está en rampa
120 a 330 ° C [ 34 , 35 ]. identi fi cation of PCDDs/Fs is typically achieved by isotopic dilution, where at
least two ions per congener could be identi fi ed. Techniques incorporating gas chromatography
coupled to Tandem Mass Spectrometry (GC-QITMS/
3
Tendencias en Medio Ambiente Química Analítica 17 (2018) 1-13
MS) provide excellent sensitivity and linearity [ 47 – 50 ]. In the case of low-resolution GC/MS two
mass-selected congeners from the molecular cluster were monitored in a single ion monitoring (SIM).
Congeners are identi fi ed based on isotopic ratio and retention time in both techniques.
In 2000 the European Union (EU) was pushed to start an e ffi cient monitoring program to ensure
the proper quality of European food and feed. As a result, the European Commission (EC) began to
propose legislation to regulate Maximum Residual Levels (MLs) for PCDDs, PCDFs and DL-PCBs in
food stu ff s y piensos, así como directrices para métodos analíticos para apoyar e implementar el
control continuo de alimentos y piensos. Un nuevo reglamento se publicó en 2006 (2006/794 / CE) en
un control aleatorio de la presencia de dioxinas, PCB similares a las dioxinas y PCB no similares a
las dioxinas, los Estados miembros sobre la base de criterios de fi definido por las Recomendaciones
2004/704 / CE y 2004/705 / CE de piensos y alimentos, respectivamente, de la Comisión [ 51 , 52 ]. La
especificación aceptada fi límite c de cuanti fi catiónico (LOQ) de un congénere individual es la
concentración de un analito en el extracto de una muestra que produce una respuesta instrumental a
dos di ff iones Erent a ser monitorizados con una relación S / N (señal / ruido) de 3: 1 para la señal
menos sensible y ful fi lment de los requisitos básicos [ 51 , 52 ]. Recomendación 2006/794 / CE sugiere
adoptar picogramo / g (pg / g) cuando informar de los resultados de dioxinas, furanos y PCBs
similares a las dioxinas, y nanogramo / g para los PCB no similares a las dioxinas. la Ciencia fi Panel c
CONTAM de la AESA), relacionado con la presencia de NDL-PCB en piensos y alimentos, se dio
cuenta de que la suma de los seis PCB indicadores representaba aproximadamente el 50% del total
Nondioxin PCB similares a las presentes en los alimentos [ 52 ]. Recientemente, los reglamentos
europeos que se establecen los métodos de muestreo y análisis para la junta de la UE FFI el control
oficial de los niveles de PCDD / Fs en alimentos y piensos han sido recientemente modificada por la
UE (. Reglamento nº 589/2014 y 709/2014) con una actualización importante es el reconocimiento de
la cromatografía de gases (GC) de triple cuadrupolo espectrometría de masas (GC - QQQMS / MS)
como con fi confirmatoria herramienta para comprobar el cumplimiento de los niveles máximos (ML) [ 53
]. Estas revisiones se han iniciado ya que esta tecnología ahora exhibe un comportamiento similar a
GC (sector magnético) espectrometría de masas de alta resolución (GC-HRMS) [ 53 ]. Otros métodos
que incluyen chromatographytime gas de Florida espectrometría de masas de vuelo (GC x GC
TOFMS) [ 54 - 57 ] Y cromatografía de gases Transformada de Fourier Ion Cyclortron Resonancia
espectrometría de masas (GC-FTICRMS) se han utilizado y desarrollado [ 48 , 49 , 58 ].
Otros estudios han probado métodos no utilizados comúnmente y obtenido resultados positivos.
Por ejemplo, un estudios canadienses, han observado que se obtiene una mejor sensibilidad cuando
se aplica un cromatógrafo de gases-tandem cuadrupolo-transformada de Fourier ciclotrón de iones
espectrómetro de masas de resonancia (GC - MS / MS-FTICRMS). Este método se utiliza para
investigar clorados-dioxinas / furanos (CDD / CDF), así como las dioxinas halogenados mixtos /
gases capilar [ 59 ]. Otro estudio realizado en los Estados Unidos calcula el índice de emisiones
usando la base de datos de la EPA y la emisión anual se informó en ng EQT / año usando un HRGC
/ HRMS operados en modo de ionización electrónica positiva con una resolución de masa por encima
de 10, 000 siguiendo las directrices establecidas por la EPA [ 60 ]. Además, una publicación
interesante, informó sobre las medidas cuantitativas de las dioxinas y los furanos utilizando sólo la
espectroscopia láser de absorción infrarroja se presentan en un modo de absorción directa, por lo
que es el fi estudio de primera para informar sobre el uso potencial de la espectroscopia IR [ 61 ].
Debido a su amplia presencia en el medio ambiente, PCDD y PCDF se han convertido en una
medida rutinaria por las agencias ambientales de varios países de todo el mundo. Varios métodos
han sido informados por la Agencia de Protección Ambiental de Estados Unidos (USEPA) para el
análisis de dioxinas y furanos en compartimentos ambientales como se muestra en tabla 1 . Según
Harrad, existen otros numerosos métodos que pueden utilizarse para analizar muestras de dioxinas y
furanos en diversas condiciones [ 27 ]. Por ejemplo, el método USEPA 8280 es el método más
adecuada que se utiliza para la detección de trazas de dioxinas en el aire. rea Wittich FFI rms que la
naturaleza de la muestra determina la cantidad máxima
S. Kanan, F. Samara
tabla 1
Agencia de Protección Ambiental de Estados Unidos (USEPA) para el análisis de dioxinas y furanos en los compartimentos ambientales.
Método Los compuestos de interés
Método USEPA tetra a dibezo-furanos octa-clorado (CDF) y dibenzo-p-dioxinas (CDDs)
1613
Método USEPA 2,3,7,8-tetraclorodibenzo-p-dioxina (2,3,7,8-TCDD), 2,3,7,8tetrachlorodibenzofuran (2,3,7,8-TCDF), y
8280 el 2,3, 7,8-sustituido penta-, hexa-, hepta-, y octo-clorados dibenzo p-dioxinas (PCDD) y
dibenzofuranos (PCDF)
USEPA Method tetra- through octachlorinated homologues; PCDDs), and polychlorinated dibenzofurans (tetra-
8290 through octachlorinated homologues; PCDFs)
Method 23 and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/PCDFs), polybrominated
TO-9 dibenzo-p-dioxins and dibenzofurans (PBDDs/PBDFs), and bromo/chloro dibenzo-p-dioxins and
dibenzofurans (BCDDs/BCDFs)
método apropiado que se puede utilizar. Lodos, líquidos, aire y muestras de suelo funcionan mejor en
di ff erent methods based on their physical nature [ 62 ]. However, they have a conventional method of
presenting their
fi ndings in a way that is easy to understand after an interpretation of the results has been made.
4. Photocatalysis and/or removal techniques in environmental compartments
Several photocatalysis studies have been explored in order to reduce dioxins and furans in the
environment. Kostantinov et al. used a lowpressure ultraviolet mercury lamp to destroy dioxin-like
compounds, both as individual congeners and in actual waste analytical samples. Experiments with
1,6-[3H]-2,3,7,8-TCDD revealed that the principal photolytic pathway involves cleavage of C e O bonds
rather than C e Cl bonds, giving chlorinated hydroxydiphenyl ethers as the initial products. The
photolysis products from 2,3,7,8-TCDD do not bind to either the rat hepatic Ah receptor or the
estrogen receptor in vitro, making it unlikely that the products from the UV treatment of PCDD/PCDF
in laboratory waste will show either Ah or estrogen receptor-mediated toxicological e ff ects [ 70 ].
The photolytic activities of dibenzo-p-dioxins and − furans in methanol and n-hexane were found
to follow fi rst order decay rates. The photolysis rate constants in n-hexane increased with increasing
number of halogen atoms in the PCDD and PCDF framework. For example, the monobrominated and
the octabrominated derivatives showed rate constants of 4.5×10 − 4 s − 1 and 7.7×10 − 3 s − 1, respectively.
In addition, the dibrominated derivative shows a rate constant of
4.0×10 − 3 s − 1 while the heptabrominated furan has a rate constant of
8.3×10 − 2 s − 1. Photolysis in methanol is nearly six times slower than in n-hexane and the bromine
compounds were identi fi ed to react by an order of magnitude faster than the chlorine analogues [ 71 ].
It was found that pure water or 60% acetonitrile/water solutions of
2, 7-DCDD and 1, 2, 7, 8-TCDD were photodegraded faster at 300 nm than their PCDF analogues.
PCDD compounds have higher photodegradation rates in acetonitrile/water than in pure water. For
example, the photodegradation rate constants for individual PCDDs and PCDFs varied from 8.9×10 − 2 min
− 1 for DCDD in pure water to
1.0×10 − 3 min − 1 for OCDD in 60% acetonitrile water. Lower chlorinated PCDDs and PCDFs accounted
for less than 18% of the loss of the parent compounds [ 72 , 73 ]. Kim et al., have found that PCDD/Fs
on particulate can be treated by heat activated persulfate (HAP) where the removal rates of PCDD/Fs
was found to decrease as the numbers of chlorines increased by HAP. In addition, PCDD/Fs on the fi ne
particle were removed better than on the coarse particle with more persulfate being consumed to
remove high chlorinated compounds [ 72 ].
Several catalysts such hydroxyl radical source [ 74 , 75 ], metal based materials were identi fi ed to
be active catalysts for the photodegradation of organic pollutants especially polyaromatic hydrocarbon
and pesticides. Materials including TiO 2 [ 76 , 77 ], ZnO [ 76 , 77 ], SnO 2 [ 78 ], Silver doped zeolites [ 79 – 85microorganismo
],
gold doped zeolites [ 86 – 88 ], and mixed metals
4
Trends in Environmental Analytical Chemistry 17 (2018) 1–13
Matriz ambiental Las referencias de herramientas analíticas
sedimento, agua, lodo, el tejido, el suelo HRMS / HRGC [ 63 - sesenta y cinco ]
agua, suelo, Florida y ash, and chemical waste samples, HRGC/LRMS [ 27 , 66 ]
including stillbottom, fuel oil, and sludge matrices
variety of environmental matrices HRGC/HRMS [ 67 , 68 ]
ambient air including stack gas emissions, fl y ash, soil, HRGC/HRMS [ 69 ]
sediments, water, and fi sh and human tissue
doped zeolites [ 89 ] are well studied in literature. Since the presence of the hydroxyl radicals (OH) are
expected to be an important removal pathway of polychlorinated dibenzo-p-dioxins and dibenzofurans
(PCDD/F) in the atmosphere, Wu et al. have developed a system to measure the rate constants of the
gas-phase reactions of OH with semivolatile organic compounds using on-line mass spectrometry.
OH reaction rate constants were determined in helium for 1,2,3,4-tetrachlorodibenzo-pdioxin at 373 – 432
K using a heated quartz reaction chamber [ 76 ]. For example, under 254 nm UV source, photolysis of
O3
in the presence of H 2 O and the photolysis of H 2 O 2 served as OH sources. The reaction rate constant
of 1,2,3,4- tetrachlorodibenzo-p-dioxin with OH was 8.5×10 − 13 cm 3 s − 1 at 298 K [ 74 , 75 ]. The e ff ect del
radical OH sobre la fotodegradación de varios dioxina clorado se ilustra en la Figura 2 [ 88 ] Con las
constantes de velocidad para di ff sistemas catalizados Erent se resumen en Tabla 2 .
Wu et al. han informado de la fotolisis directa y procesos fotocatalíticos para la 2,3,7,8-TCDD y
1,2,3,6,7,8-HxCDD bajo TiO 2, ZnO y SnO _ 2 catalizadores. de SnO 2 mostraron una baja actividad
debido a que la energía de la luz UV fue parcial para excitar de SnO 2 en un solo sistema de
catalizador. En este caso, de SnO 2 realizado como un eliminador de fotogenerada de electrones
apropiado en sistemas catalizadores acoplados [ 78 ]. TiO 2 fi lm bajo irradiación con 365 nm UV se
utilizó para estos experimentos y los compuestos se inmovilizaron sobre TiO 2 / fase sólida. Sin
producto PCDD / PCDF 2,3,7,8-sustituido se detectaron en proceso fotocatalítico en las condiciones
experimentales. Las constantes de velocidad de reacción eran 0.3256 h - 1 para
2,3,7,8-TCDD (2000 ng) en UV / TiO 2 de reacción, 0,2474 h - 1 para
1,2,3,6,7,8-HxCDD (2000 ng) en UV / TiO 2 de reacción, y 0,0666 h - 1 para
1,2,3,6,7,8-HxCDD (50 ng) en directo irradiación UV [ 76 , 77 ].
Por otra parte, modi plata fi ed zeolita Y ha demostrado capaz de degradar
derivado F, en una solución de metanol 2,3,7,8-TCDD, los PCDD más tóxica / / THF [ 95 , 96 ]. La
presencia de plata cargados en la zeolita se descompone 2,3,7,8-TCDD por 86% después de la
irradiación UV 254 nm durante 6 h. Este es un incremento notable sobre la irradiación UV solo que
reducen la concentración de TCDD en un 28% dentro del mismo marco de tiempo. Los catalizadores
de plata Y también conducen a una disminución en la intensidad de la banda de emisión desde la
2,3,7,8-TCDF absorbido en el catalizador ' s superficie. El importe de la adsorbido 2,3,7,8-TCDF en el
di ff catalizadores Erent Agy llegaron a
18.9 - 37.9% de su concentración inicial, respectivamente. ELISA mostró que en contraste con el resto
de las muestras, la OD de las muestras TCDF y TCDD se irradia con 254 nm en presencia de
catalizador AgY2 fue alta en 40 minutos lo que sugiere una disminución de la toxicidad de los
productos de degradación [ 95 , 96 ]. Isosaari et al. han investigado el correo ff ect de aceite de oliva en
la PCDD fotodegradación / Fs en el suelo aserradero contaminada.
2,3,7,8-TCDD se redujo en la concentración en un 59% y el EQT-OMS en el suelo contaminado
aserradero se redujo en un 48% después de la mezcla del suelo con dos dosis (20 + 20%) de aceite
de oliva y la exposición a la luz solar durante cuatro semanas [ 71 ].
los fi primer informe de la degradación de PCDD altamente clorados y los PCDF por un
se realizó por Takada et al. usando los hongos de pudrición blanca. La degradación
de una mezcla de 10 derivados de tetra- a CDDs octa y CDCs por el hongo de la pudrición blanca phanerochaete
sordida YK-624
S. Kanan, F. Samara Tendencias en Medio Ambiente Química Analítica 17 (2018) 1-13

Figura 2. Vías de adición de radicales OH en HpCDD y OCDD para formar un

hydroxycyclohexadienyl [radical 90 ].

Various studies have indicated that PCDD/F compounds are subjected to biodegradation in the
Tabla 2
environment as part of the natural chlorine cycle where lower chlorinated dioxins can be degraded by
Un resumen de las constantes de velocidad determinados experimentalmente de congéneres de PCDD individuales en virtud de di ff Erent
aerobic bacteria at high percentages. In his article, Field et al. provided an extensive review of the
condiciones.
work done for the degradation of various chlorinated dioxins and furans under di ff erent
derivado estudiado Sistema / catalizador Tarifa constante k ( h - 1) referencias microorganisms [ 98 ]. The overall pathway shown in Fig. 3 implica ciclos de oxidación por la lignina
peroxidasa (IiGP) y / o manganeso peroxidasa (MnP) quinonas que forman, seguido por reducción a
1, 2, 3, 6, 7, 8-HxCDD UV 0.07 [ 77 ]
hidroquinonas o catecoles y metilaciones posteriores a methoxybenzenes. 124 THB está sujeto al
UV 0.06 [ 76 ]
Luz de sol 0.01 [ 91 ] anillo de escisión, lo que podría conducir a la mineralización a CO 2 [ 98 ].
UV / ZnO 3.28 [ 76 ]
UV / de SnO 2 3.19 [ 76 ]
UV / ZnO-de SnO 2 7,47 [ 78 ]
UV / TiO 2 Muy rapido [ 76 ]

OCDD UV 0.06 [ 73 ]
UV 0.17 [ 92 ] 5. PCDD y PCDF en el entorno de varios países
UV 0.01 [ 92 ]
UV 1.00 [ 94 ]
Para evaluar la situación actual de la presencia de PCDD, PCDF y PCB DL en el medio
Luz de sol <0,01 [ 91 ]
ambiente mundial, se incluyeron los estudios seleccionados de varios países en este estudio. Los
Luz de sol 0.16 [ 92 ]
UV / ZnO 0.74 [ 76 ] estudios incluyen las principales fuentes y las concentraciones de corriente que se encuentran en las
UV / de SnO 2 0.28 [ 76 ] especificadas fi c estudios en los países industrializados, como Estados Unidos, Canadá, Europa,
UV / ZnO-de SnO 2 1.41 [ 78 ]
China, Japón y Oriente Medio. Aunque, vasta literatura está disponible para la mayoría de los países,
UV / TiO 2 0.12 [ 90 ]
se discuten a continuación estudios sólo seleccionados.
UV / TiO 2 5.30 [ 76 ]
O3 0.37 [ 94 ]
UV / O 3 1.09 [ 94 ]
UV / H 2 O 2 0.04 [ 93 ]
5.1. Los estudios de dioxinas en los Estados Unidos
2,3,7,8-TCDD UV 0.09 [ 93 ]
Luz de sol 0.04 [ 92 ]
Debido a su formación como subproductos accidentales y persistencia; PCDD, PCDF y PCB DL
1,2,3,4,7,8-HxCDD UV 0.01 [ 93 ]
todavía están presentes en cantidades considerables en el medio ambiente. Por ejemplo, en 2011 el
UV 0.18 [ 92 ]
análisis del aire mostraron que las concentraciones de dioxinas fueron los más altos durante ese
Luz de sol 0.10 [ 92 ]
tiempo que nunca se ha informado en la historia [ 11 ]. En un correo ff ORT para determinar la cantidad
de dioxinas en la atmósfera, la EPA ha implementado un sistema conocido como la Red de
Monitoreo de dioxinas Nacional del aire (NDAMN). El sistema se hizo funcionar de partida de 1998
was studied in a stationary low-nitrogen medium. The results suggest that white rot fungus is able to hasta 2004, donde se recogieron más de 600 muestras y se analizaron [ 99 ].
degrade both PCDDs and PCDFs with percent degradation values of approximately 40 (TCDD) to
76% (HxCDD) and 45 (TCDF) to 70 (HxCDF), respectively [ 97 ].
Además, con el fin de calcular un índice de emisión de dioxinas, 40

5
S. Kanan, F. Samara
Fig. 3. Proposed pathway of 2,7-dichlorodibenzo- p- dioxin (2,7-DCDD) degradation by the white-rot fungus,
phanerochaete chrysosporium [ 98 ].
di ff fueron entrevistados participa Erent de varios lugares en los EE.UU.. El índice de emisión se
calcula utilizando la base de datos EPA. El di ff muestras Erent recogidos de las casas incluyen varias
bolsas de vacío que se congelaron a - 20 ° C hasta su análisis [ 60 ]. Moreover, Henri H. Dwyer,
examined the release of dioxins from controlled industrial and open burning sources. These sources
were later classi fi ed into: waste incineration, waste to energy, electricity and heat generation,
metallurgical processes, as well as non-controlled smaller scale combustion processes for open
burning. The results stated that the greatest emissions of dioxins were released from electricity and
heat generating plants, which contributed a total of 66.2% of these emissions, followed by metallurgic
processes, waste incineration and the WTE industry. Open burning sources contributed 7.2% of the
emissions, with land fi ll
fi res contributing the most by 44% followed by forest fi res at 28% [ 100 ]. In contrast, for the open
source emissions of dioxins, the values reported showed an increase of 43%. This is mainly due to
the various large forest fi res and land fi lls that account for about 77% of the major open source
emissions and a 93% increase of the emissions. This increase is due to the higher temperatures in
forest fi res and better reporting of the land fi ll and forest fi res [ 100 ].
Gilbreath and McKee conducted a research on urban watersheds in San Francisco to determine
the concentration of chemicals such as dioxins, organochlorine pesticides, and pyrethroids. The
analyzed samples, con fi rmed the presence of seven types of dioxins which have a
6
Trends in Environmental Analytical Chemistry 17 (2018) 1–13
toxic equivalence factor (TEFs) assigned by the World Health Organization (WHO), ranging over an
order of magnitude between low and storm fl ow conditions (0.226 – 6.26 ng/L) with the fl ow of dioxins
and furans during storm is reported to be 6.26m 3/ s during storm fl ow and 0.226m 3/ s during low fl ow,
when no storm is occurring [ 13 ]. According to a dioxin exposure study conducted by the University of
Michigan (UMDES), it was observed that the soil and fi sh contamination in the Tittabawassee River fl oodplain
in Midland lead to increased levels of dioxins and furans in blood levels of local residents. A total
number of 29 PCDD, PCDF, and PCB congeners with dioxin-like activity were used to predict their
body burdens [ 101 ]. It was primarily based on dioxin contamination in blood cells of the surrounding
human population. During this study they collected questionnaires, blood, dust, and soil samples of
731 people [ 101 ]. The results of this study, provided insight on the exposure pathways by which
dioxins in soils, sediments,
fi sh and homegrown produce lead to increased body burdens of these compounds [ 101 ].
It was shown that the Saginaw River and Bay received discharges from 87 di ff erent industrial
facilities as well as 127 wastewater treatment plants, and the Tittabawassee River is the largest
tributary to the Saginaw River [ 102 ]. Pollution with PCDD/Fs in this area as considered one of the
major chemical concerns identi fi ed by the Michigan Department of Public Health. Twelve di ff erent fi shes
from the Tittabawassee and Saginaw Rivers were measured for their concentrations of PCDD/Fs and
PCBs, in which resulted in di ff erent concentrations as the lipid content in each fi sh varied from one
species to another. In speci fi c, the carp fi sh received the highest Σ PCDD/Fs and Σ TEQs compared to
other species (i.e. Σ TEQs=54 ± 59 pg/g ww). Next, followed the channel cat fi sh and the northern pike
with a Σ TEQs value of (34 ± 28 pg/g ww) and (13 ± 11 pg/g ww), respectively [ 102 ]. The least
concentrations of Σ TEQs were found in bluegill with a Σ TEQs value of (1.7 ± 1.5 pg/g ww) [ 102 ].
The emissions of dioxins from various sources such as waste incineration and asphalt
production in the United States during 1987 to 2012 were evaluated [ 100 ]. The study indicates that
the emissions of dioxins have decreased considerably, as the sources of emissions have been under
control. However, some emissions have increased even under control. For instance, diesel fuel
emissions under electricity and heat generation have increased from 70 g TEQ/year in 1987 to 118 g
TEQ/year in 2012. On the other hand, sewage sludge incineration under waste incineration category
decreased from 6 g TEQ/year in 1987 to 0 g TEQ/year in 2012 [ 100 ]. The detection of the dioxins
concentrations in water and marine environments is important, because dioxins can be taken up by
plants and fi sh and could later biomagni fi ed to humans [ 103 ]. As dioxins are hydrophobic, these
compounds are adsorbed on particulate matter in aquatic settings, resulting in very low
concentrations in dissolved phases, in the nanometer or picometer per liter range. Single phase
samplers can also be used, consisting of low density polyethylene (LPDE) strip and silicone rubber,
as they involve easier sample processing. Lastly, the continuous integrative fl ow sampler (CFIS) is a
newly designed sampler, involving the use of a pump, powered by batteries that can be fully
submersed, with sampling rates that remain una ff ected by water turbulence or velocity [ 104 ]. Using
such methods, the concentrations of dioxins in water could be measured.
5.2. Dioxin studies in Canada
Burning of household garbage has been identi fi ed as the largest source of dioxin emissions in
Ontario where open burning of agricultural plastics is one of the main contributors [ 105 ]. Burning
10,000 pounds of agricultural plastic has the potential to contaminate
75,000 kg of soil from exposure to dioxins, based on Canadian Soil Quality Guidelines. In Alberta
alone, it is estimated that more than 20 million pounds of agricultural plastics are sold annually, and
that the predominant method of waste management is open burning. If half of
S. Kanan, F. Samara
this plastic is handled through on-site burning, it has the potential to contaminate 75 million kg of soil
due to dioxins exposure [ 105 ]. The contamination of soil has its pathways for human by the
consumption within a food web such as vegetation to grazing animals to humans. According to a
comprehensive risk assessment study for human and ecological risk that was undertaken at a site in
southern Ontario, the average soil for the most toxic dioxin, TCDD, is 11.1 pg/g DW [ 106 ].
Discharges of dioxins and furans to the Canadian aquatic environment reached non-measurable
levels in 1995 which made the point source discharges to water to be the target of the Canadian
federal and provincial regulation, as well as industry innovation to change [ 107 , 108 ]. As a result,
many studies were made in Canada to determine the concentrations of dioxins and furans in its
contaminated water. One of these studies was conducted to test the water contamination of the Great
Lakes by testing the lake trout because of its presence across all Great Lakes and high lipid content
which makes it suitable for monitoring levels of organic contaminants [ 23 ]. The lake trout was frozen
and tested through a speci fi c analysis and then the amount of PCDDs and PCDFs were determined in
terms of TEQs. The study showed that the highest TEQs were observed in Lake Ontario Lake trout
with values ranging from 22 to 54 pg/g [ 23 ]. However, the temporal data from 1989 to 1999 depict a
promising scenario suggesting that TEQs in Lake Ontario Lake trout are decreasing annually at
approximately 1.5 pg/g [ 23 ]. This high contamination amount in lake trout shows that the water of
Great lakes is also signi fi cantly a ff ected by these compounds. The concentration of PCDDs/PCDFs in
poultry samples in Canada was
2.6 pg I-TEQ/g [ 109 ]. Lastly, a study was made in Canada to account for the PCDDs and PCDFs
concentrations (pg I-TEQ/g fat) in human milk and showed that the concentration in years 1986 – 1987
was 15 pg I-TEQ/g fat [ 109 ].
Atmospheric transport is a primary pathway for the transfer of PCDDs and PCDFs to terrestrial
and aquatic ecosystems via deposition which makes it essential for the Canadian government to test
the ambient air for the contamination of these compounds in air. In 1981, the Canadian tested
ambient air had a range of dioxins and furans contamination in a range of 0.4 – 36.7 pg/m 3 [ 110 ]. This
range was due to taking samples from di ff erent locations over the country, where industrial areas had
a higher amount of dioxins and furans than other areas.
5.3. Dioxin studies in Europe
Analysis of dioxin/furans and dioxin-like PCBs (DL-PCBs) were performed in Germany in
accordance to the requirements of Commission Regulation methods of sampling and analysis for the
o ffi-
cial control of levels of DL-PCBs in certain foodstu ff s including sheep [ 111 ]. Results show that 72 out
of 77 investigated sheep liver samples exceeded the European maximum tolerance level of 6.0 pg
WHOPCDD/F-TEQ g − 1 fat with 71 samples also exceeded the cumulative maximum tolerance level of
12.0 pg WHO-PCDD/F-PCB-TEQ g − 1 fat set in the EU for the sum of PCDD/PCDFs and DL-PCBs in
livers of sheep and derived products. Results show no signi fi cant correlation between the levels of
PCDD/PCDFs or DL-PCBs and the fat content of the samples. However, the highest concentrations
where detected in female sheep livers, indicating that gender might play a role in the bioaccumulation
of this POPs. In addition, no correlation was determined between their age and the burden of their
livers with PCDD/PCDFs or DLPCBs [ 111 ].
In France, food samples were monitored by the ‘ Market Basket ’
which gathers data on almost all food products mostly of animal origin and some fruit, vegetables, and
vegetable oils [ 112 ]. Results showed that in meat products 85% of the chemicals present are
DL-PCBs. In dairy products and eggs, the proportion PCDD/F and DL-PCBs is better balanced: 30:70
and 45:55%, respectively. Sea (wild and farmed) and freshwater fi sh have a total concentration of
between 2.7 and 2.9 pg TEQ g − 1 fresh weight where, DL-PCBs account for 80 – 85% of total
7
Trends in Environmental Analytical Chemistry 17 (2018) 1–13
contamination for sea fi sh and freshwater fi sh and 55 – 75% for other
fi sh products. Reported concentrations of PCDD/F and DL-PCB in Vegetable products did not exceed
0.01 pg WHO-TEQ g − 1 fresh weights [ 112 ]. Moreover, in Netherlands, the average concentration of
dioxins and DL-PCBs in fi sh was found to be higher than in meat products. Results show that the
levels of PCDDs and PCDFs in most vegetable products are close to or lower than low-fat animal
products such as beef [ 113 ]. The distribution of compound in soil is more heterogeneous than in air
which causes di ff erence concentration in samples [ 113 ].
France is known to be the biggest emitter of dioxins in Europe since they lack regulations
regarding PCDD/F emissions form waste incinerators in plants (same with Italy and Spain) [ 114 , 115 ].
As of 2005, most of the industrial processes in Germany were required, by law, to reduce emissions
of dioxins from 400 g to less than 0.5 g in air, and have an emission limit of 0.1 ng I-TEQ/m 3 [ 34 , 115 , 116
]. Moreover, it was found that the introduction of waste incineration actually reduced the potential
excretion of dioxins that would have otherwise been produced naturally from forest fi res due to
extensive fi lter units that prevent the release of high metal content chemicals.
Another good matrix to study is ‘ street dust ’ which refers to the deposited dust on paved surfaces
at industrial sites and next to roads [ 33 ]. Although limited data is published a distinctive trend was
found in West North Rhine-Westphalia, Germany, relating particle sizes of the dust and increasing
concentrations of PCBs and PCDD/Fs in street dusts [ 117 ]. Water is also an important matrix to study
when investigating the contamination of dioxins and furans. Although poorly soluble in water, some of
these low concentrations can still exist in drinking and surface waters [ 35 ]. Most of the releases from
the incineration and waste sites can easily contaminate the water exerted back into the environment,
causing bioconcentration and eventually biomagni fi cation in the food chains. The Baltic Sea is known
to be one of the largest rivers in Central Europe, which unfortunately, is one of the areas most
contaminated by POPs including PCDD/Fs. Because of the possibility of high toxic exposures, it is
forbidden to use the fi sh obtained from this region for human consumption [ 118 ]. In Germany, the
river Elbe was also found to entail high levels of PCDD/Fs based on sampling conducted on eels and
white fi sh. Usually, the highest sources of dioxins and furans that are released to land in Europe come
from pesticide production, accidental fi res and again, incineration of Municipal Solid Wastes (MSW) [ 115
].
Comparative sample results from Germany, France, and Netherlands were investigated to
determine concentration levels of dioxins and furans that are found in street dust, raw cow milk, home
produced eggs, respectively. Table 3 summarizes the results obtained where street dust is observed
to have the highest concentration of PCDD/PCDFs. However, when food products were compared,
home produced eggs had a much higher concentration than raw cow milk, which might be due to fat
content.
In Greece, a country where industrial emission sources are very limited, the most important
source of PCDDs/Fs is considered to be the uncontrolled combustion of municipal solid waste in open
land fi lls. PCDD/F and PCB contamination levels in blood and human milk from Greece samples were
low compared to the previously reported dioxin data from other European countries giving no
indication of a particular health risk. Furthermore, Athens had signi fi cantly higher total PCB
concentrations compared to the rural region of Kozan [ 120 , 121 ]. Several studies, have reported the
presence of PCDD/Fs pollution in the region. A study on the Rhone River, reported that it annually
discharges an average of 1040m 3/ s downstream. Concentration measurements were detected using
high resolution HRGC/HRMS for a total of 7 PCDDs and 10 PCDFs [ 122 ]. Other studies have
reported on the presence of dioxins and furans soil samples taken from a sawmill site in Sweden. In
the site, chlorophenols (CPs) were being used during the 1950 ′ s – 1970 ′ s, where dipping was used for
short term prevention of rot and blue staining of wood (newly sawn timber) [ 123 ]. The most common
preservatives at that time were mixtures of chlorophenols which contained
S. Kanan, F. Samara Trends in Environmental Analytical Chemistry 17 (2018) 1–13

Table 3
PCDDs/Fs concentrations detected in samples from European countries.

Sampling location Sampling Sampling Method Sampling Site/type No. of Samples dl-PCB TEQ PCDD/PCDF Ref.
Matrix [ng/ kg] TEQ [ng/kg]

North Rhine- Street Dust Pressurized Liquid Extraction and Gas Rural ® 6 6.5 2.4 [ 117 ]
WestphaliaGermany Chromatography coupled to Mass Spectrometry Urban (U) 16 6.8 4.4 [ 117 ]
Industrially In fl uenced Urban 19 6.4 3.6 [ 117 ]
(UI)
France Raw Cow Milk Liquid-liquid Extraction and Gas 93 plants from 17 di ff erent 239 0.57 0.33 [ 119 ]
Chromatography coupled with High Resolution dairy groups
Mass Spectrometry
Netherland Home Produced Gas Chromatography and High Resolution Mass 62 addresses from 20 eggs from each 2.0 2.8 [7]
Eggs Spectrometry various regions participant

PCDD/Fs produced during the manufacturing process of preservatives [ 123 ]. Therefore, the most
recent Swedish guidelines documented by Henriksson et al., allocate a concentration of 20 ng/kg dw
WHO-TEQ to classify the land used for habitation and a concentration between 20 ng/kg dw
WHO-TEQ and 200 ng/kg dw WHO-TEQ to classify land used for industrial purposes [ 123 ].
In Turkey, PCDD/Fs and PCBs are typically disposed into the black sea by industries, in addition
to, contamination by countries surrounding the Black Sea. This increase in aquatic contamination has
resulted in accumulation of harmful residues of PCDD/PCDFs and PCBs in the aquatic organism in
the marine environment which directly affects the food chain [ 124 ]. Four sea bass samples were
studied, three sea bream samples and one imported fi sh feed sample used in one of the sea bass
farms. Persistent organohalogen compounds have a strong tendency to accumulate in fat, which is
why concentrations are usually normalized on a fat basis. Hence, the highest levels of PCDDs,
PCDFs and PCBs were observed in sea bream, as expected because of the higher lipid content [ 124 ].
be concluded that the concentrations of dioxins and furans in the ambient air of China are comparable
with the urban air of other countries like Athens (166.6 – 701.5 fg/m 3) and Brazil (47 – 751 pg TEQ/m 3)
[ 130 , 131 ].
Reports suggest that 16.1% of China ’ s soil su ff ered from contamination (BBC Report, 2016).
One of the major soil contaminants in China are dioxins and furans that are formed during industrial
processes and have the potential to become harmful to the human health and environment [ 132 ]. A
study using combustion technology reported on the long-monitoring of dioxins and furans around
medical waste incinerators in the North of Zhejiang, China. For this study, about 10 g of soil were
collected on a dry basis, and extracted using Selective Pressured Liquid Extraction (SPLE). Since
2007, studies showed that the dioxin and furans concentrations increased throughout the years due to
of the increase of pesticides, solvents, hydrocarbons, and factory emissions [ 133 , 134 ].

During the last two decades, Pearl River Delta (PRD) has become one of the most prosperous
regions in China after undergoing a rapid economic, industrial and agricultural growth. The population
increased from 962 million in 1978 to 1314 million in 2006, which also resulted in an increase in the

5.4. Dioxin studies in China demand of agricultural products. As a result, the total uses of chemical pesticides and fertilizers
increased signi fi cantly and thus the amount of these pesticidal POPs generated increased as well.

China is known to have several studies targeting the presence of dioxins and furans. There is Because the generation of solid waste is increasing, large municipal solid wastes incinerators are

more than ten analytical laboratories with HRGC/HRMS and quali fi ed for the quantitative detection of needed to handle the tremendous amounts of waste generated every day. In the case of water, about

dioxins. Data is constantly published on the current levels of PCDD/Fs in soil, sediments and ambient one third of the industrial waste water and more than 90 percent of household sewage in China is

air samples around China. In 1999, State Environmental Protection Administration (SEPA) released into rivers and lakes without being treated. In the summer of 2011, the China government

constructed a dioxin monitoring laboratory in the National Research Centre for Environmental reported that 43 percent of the state-monitored rivers are so polluted that are considered to be

Analysis and Measurement to study the current analysis and sampling methods for main dioxin unsuitable for human contact [ 135 ].

sources in order to propose measures for controlling dioxin pollution [ 125 ]. An o ffi cial inventory setup
by Lin et al. showed that the emission of dioxin from power generation and heat supply, waste
incineration, mining, and transportation accounted to a total of about 10,237 g TEQ [ 126 ]. The
concentration of PCDD/Fs ranged from 275 to 10,780 fg/m 3 ( 18 – 644 fg ITEQ/m 3) with an average
value of 4355 fg/m 3 ( 268 fg I-TEQ/m 3) for three districts in Beijing. Li et al. found signi fi cant Studies showed that water bodies located near a highly industrialized zone are more prone to

concentrations of PCDD/Fs and PBDD/Fs in the ambient air for four districts of Shanghai [ 127 ].
POPs contamination. Gulkowska et
al. analyzed Per fl uorooctanesulfonic acid (PFOS) and
Per fl uorooctanoic acid (PFOA) in seafood samples purchased from fi sh markets in Zhoushan and
Guangzhou, and China, reporting that PFOS were detected in all samples including fi sh, oysters,
crabs, mussels, clams and mollusks [ 136 ]. However, the concentrations weren ’ t high enough to cause
immediate health risk to people living in the coastal region of China. Even though no immediate health
risk was detected, it is important to closely and regularly monitor food safety in China.

Gas/particle partitioning of PCDD/Fs was measured by Xu et al. from April 2007 to January 2008
in a satellite town of Eastern China [ 128 ]. The results concluded that the PCDD/Fs levels were higher
during the winter season when compared to the summer season with a value in the range of 86 – 3030
fg/m 3. Choi et al. measured PCDD/Fs level in 142 air samples of Hong Kong [ 129 ]. The average
PCDD/Fs concentration in the air samples obtained from Hong Kong from January 2004 to March
2005 for Tap Mun, Yuen Long, and Tsuen Wan were 1724 fg TEQ/m 3, 2927 fg TEQ/m 3, and 1875 fg
TEQ/m 3, respectively. The level of PCDD/Fs in the ambient air of Dalian (2.72 fg TEQ/m 3) was found to
be lower than the values obtained in Beijing, Shanghai, and Hong Kong [ 125 ]. Frommost of the data
available, it can
5.5. Dioxin studies in Japan
Studies conducted in Japan reveal that the most important sources for PCDDs/PCDFs are
municipal and hazardous waste incineration; production of iron and steel, copper, lead and zinc; and
coal consumption [ 137 ]. In speci fi c, the total dioxin emissions from the use of agrochemicals in Japan
during 1955 – 1995 were estimated to be about a few hundred thousand kg of PCDD/DFs and 250 kg
of WHO-TEQ from pentachlorophenol [ 138 ]. The annual deposition fl ux of dioxins

8
S. Kanan, F. Samara Trends in Environmental Analytical Chemistry 17 (2018) 1–13

Table 4 were still detected in river water from the deposition of rainfall at concentrations of 2.4 pg-TEQ/L/year,
Matrix of Dioxin analysis in Japan [ 142 ]. exceeding the environmental quality standard (EQS) for water in Japan of 1 pg-TEQ/L [ 144 ]. Another
study, determined the concentrations of PCDDs/Fs and DL-PCBs in dietary supplement products,
Areas in Japan (Most Matrix Concentration Common Technique of
Populated) Analysis
containing the oil of fi sh, marine mammals, or egg yolk, on the Japanese market between 2007 and

Special districts of Tokyo Air 0.2 μ g/m 3 TO-9

Water 0.4 μ g/m 3 USEPA Method 8280
2014. Their results showed that at least in 43 samples of the total of 46 samples, dioxins were
Organisms 2.0 μ g/m 3 USEPA Method 1613
detected with concentrations ranging from
Sediments 125 μ g/m 3 USEPA Method 8290
0.00015 to 67 pg TEQ/g [ 145 ].
Yokohama Air 0.1 μ g/m 3 TO-9
Water 0.3 μ g/m 3 USEPA Method 8280
Organisms 3.0 μ g/m 3 USEPA Method 1613 5.6. Dioxin studies in the Middle East
Sediments 115 μ g/m 3 USEPA Method 8290

Osaka Air 3.3 μ g/m 3 TO-9 One of the major problems with the management of chemicals in many of the Middle Eastern
Water 17.2 μ g/m 3 USEPA Method 8280 countries, is the lack of information on their hazardous characteristics. Other de fi ciencies include the
Organisms 11.1 μ g/m 3 USEPA Method 1613 absence of uni fi ed lists of POPs used, uncoordinated permitting activities, and lack of information and
Sediments 385 μ g/m 3 USEPA Method 8290
data on contamination of POPs chemicals in soils, ground water and surface water [ 146 , 147 ]. The
Nagoya Air 5 μ g/m 3 TO-9 sedimentary record of PCDD/Fs in the northwestern Arabian Gulf reconstructed from the analysis of a
Water 12.1 μ g/m 3 USEPA Method 8280
dated sediment core showed low concentrations at depths. Concentrations started to increase above
Organisms 9.1 μ g/m 3 USEPA Method 1613
the background in the mid1960s attaining a maximum of 7.5 pg/g in the early-1990s and stayed fairly
Sediments 650 μ g/m 3 USEPA Method 8290
constant thereafter [ 148 ]. The concentrations of dioxins found in sediments collected from fi ve
Sapporo Air 4 μ g/m 3 TO-9
locations in Kuwait are among the lowest reported in the literature for coastal marine sediments with
Water 8.1 μ g/m 3 USEPA Method 8280
Organisms 8.0 μ g/m 3 USEPA Method 1613 the highest concentrations found in sediments collected along a transect facing an oil loading terminal
Sediments 580 μ g/m 3 USEPA Method 8290 [ 149 ].

Kobe Air 5 μ g/m 3 TO-9

Water 15 μ g/m 3 USEPA Method 8280
Organisms 7.0 μ g/m 3 USEPA Method 1613

Atmospheric concentrations of polybrominated diphenyl ethers (PBDEs) measured at an urban

between Feb. 2012 to Feb. 2013 was 3.3 ng-toxic equivalent (TEQ)/m 2/
year with most of the dioxins in the deposition were derived from waste incinerators [ 139 ]. Samples
from Chilean city located in the middle of a complex hydrological system with several small urban
freshwater bodies along with the River Bio-Bio. The region has numerous industrial and domestic
activities that may contribute PCDD/Fs to the environment. The chemical signature of the dioxins and
furans found in all sediments which suggest that the major contribution to these sediments is likely to
be from atmospheric deposition caused by vehicle exhaust and biomass burning [ 140 ]. Compared to
other sites in Yatsushiro, Severe contamination and signi fi cant sources of PAHs in Tanoura Bay was
observed. However, dioxins and dioxin-like compounds (PCDFs, and non-and mono-ortho coplanar
PCBs) were analyzed in sediments from eight stations in Tanoura Bay with concentrations were
comparable to, or lower than at the reference sites indicating that there are no speci fi c sources of
these compounds in this Bay [ 141 ].
and a remote location over a twelvemonth period in Kuwait. The PBDE concentrations were generally
higher at the urban sites when compared to the concentrations at remote sites [ 150 ]. The most likely
source of PBDEs at the remote location is thought to be long-range transport from other regions,
whereas at the urban locations other sources such as outgassing of contaminated air emissions from
vehicles and incineration of PBDE containing waste [ 150 ]. The concentrations of PCDD/Fs and
dl-PCBs were not controlled by temperature variation resulting in the absence of any observed
seasonal pattern. A unique dioxin pro fi le was found in the ambient air samples collected from the
Umm-Al-Aish oil fi eld [ 151 , 152 ]. On the other hand, PCDDs/Fs concentrations in samples collected
from the open-burnt municipal land fi ll site at Marka/Amman have shown high concentrations of
PCDD/F ranged from 8.2 to 1470 ng TEQ (BGA)/kg

d.w. The total concentrations of PCDD/PCDF were between 685 and

Dioxin like materials have been carefully investigated in several areas in Japan. Table 4 summarizes
the sampling locations, matrix of analysis, detected contamination, and the analysis method. As
shown in
Table 4 , the amount of dioxins and furans in the water, organisms, sediments, and air is determined
by the number of industries and the nature of their activities in a region. It is also determined by the
approach used in managing wastes, especially the plastic materials and those from healthcare
facilities. Special wards of Tokyo and Yokohama are highly populated areas in Japan; however, they
have limited number of industries. The administrations in these municipalities have very strict waste
management policies which have directly contributed to very low level of dioxins and furans in these
two regions. The matrix shows that these two regions have the least detectable amounts of dioxins
and furans in air, water, organism, and sediment samples that were tested. On the other hand,
Osaka, Nagoya, Sapporo, and Kobe have high number of industries. The high industrial activity in
these regions directly correlates with the high amounts of dioxins and furans substances in the
samples that were tested as presented in Table 4 . This can be attributed to the e ffl uents and
emissions from the companies [ 142 ]. Moreover, dioxin emissions have drastically reduced after the
enactment of a law on dioxin emissions [ 143 ]. On the other hand, concentrations of dioxin
concentrations originated from combustion
112,300 ng/kg d.w which is extremely high [ 153 ].
El-Kabbanya et al. monitored PCDD/Fs in cement Kiln emissions in various fuel in Egypt. The
data indicates the presence of PCDD/F in Natural gas, mazout and coke. All of the kiln emission pro fi les
were found to be same markedly from pro fi les in ambient air where the small absolute dioxin emission
rates from the kilns suggested that kiln impacts would be detectable via ambient air monitoring [ 154 ].
In addition, PFAS concentrations in dust samples collected from three micro environments in Cairo
ranged from 1.3 to 69 ng/g with Fluorotelomer alcohols (FTOHs) being dominant. PFOS was detected
in 58% of the samples with median concentration of 0.29 ng/g while potassium per-
fl uorohexane sulfonate (PFHxS) and per fl uorodecane sulfonate (PFDS) were below detection limit [ 155
].
Surface sediments from the Napoleon Gulf and Thurston Bay on the northern shore of Lake
Victoria were analyzed for polychlorinated organic compounds. Fifteen PCDD/Fs and eleven dl-PCBs
were found in
75.5% of the samples with maximum concentrations of PCDD/Fs and dl-PCBs were 44.1 and 136 pg
g − 1 dry weight (dw), respectively [ 156 ].

Due to the presence of various resources that might enhance the polychlorinated hydrocarbons
in the Middle Eastern countries, several studies evaluated the food intake and the health associated
to food products with potential contamination. Two commercially important

9
S. Kanan, F. Samara
fi sh species, Nile perch and Nile tilapia belonging to di ff erent trophic levels were collected from the
Napoleon Gulf and Thurston Bay in Lake Victoria. Moreover, PCDDs, PCDFs and DL-PCBs were
extracted from the fi sh muscles and livers [ 157 ]. The TEQ values were found to be lower compared to
those of most fi sh samples reported in literature and were within permissible levels recommended by
the European Union, implying that the fi sh was fi t for human consumption [ 157 ]. On the other hand, it
has been reported that the Egyptian total TEQ intake due to the consumption of dairy products, fi sh/seafood
and meat is much higher than the maximum current WHO-TDI, mainly due to the high contamination
levels of PCDD/Fs and DL-PCBs reported in the dairy products [ 158 ]. Fingerprints of PAHs obtained
in the samples suggested both petrogenic and pyrolytic sources of contamination [ 159 – 161 ]. Abdallah
et al. determined concentrations of polybrominated diphenyl ethers (PBDEs), polychlorinated
biphenyls (PCBs) and some organochlorine pesticides (OCPs) in serum of Egyptian colorectal cancer
patients compared to a healthy control group. The results showed no signi fi cant di ff erences between
the levels of target contaminants in serum of cancer patients and the control group [ 158 ].
Studies on the occurrence of organohalogenated contaminants (OHCs) in human samples from
Saudi Arabia have been reported [ 162 ]. Several classes of OHCs were identi fi ed in humans from
KSA, indicating ongoing exposures to already regulated POPs. However, levels of analyzed pollutants
were generally on the lower side than studies from di ff erent countries [ 162 ]. Moreover, Batang, et al.
determined the full PCB pro fi les in edible fi sh tissues from the Saudi Red Sea coast [ 163 ]. These
levels were found to be at the lower end of reported global range and far below the prescribed
tolerance thresholds for PCBs in other countries [ 163 ]. Pesticides residues were extracted from
human milk samples collected from donor mothers in Eastern district of Saudi Arabia [ 164 ].
From an initial monitoring study of PCDD/Fs and dl-PCBs in locally produced and imported food
and feed products available across the State of Kuwait and estimation of dietary intakes, it can be
concluded that concentrations of the sum of PCDD/Fs and dl-PCBs in some of the locally produced
and imported food stu ff s and animal feed samples investigated did exceed the 2/3 of the maximum
permissible limits asset by the electrical conductivity analysis method [ 165 ].
Organochlorine pesticide (OCP) residues in several samples; comprising eggs, chicken and
meat (lamb and beef), collected from Jordan were studied [ 164 , 167 ]. The results indicated that 28%,
20%, and 49% of the examined eggs, chicken and meat samples, respectively, were contaminated
with OCP residues with HCHs and DDTs are the most prominently noticed compounds, as they were
detected at a high incidence [ 166 ]. These residues are present despite complete ban on the use of
OCPs for agricultural purposes in Jordan.
6. Concluding remarks
1 Studies of dioxins and furans entail the use of speci fi c scienti fi c
methods of extraction and analysis. Several common reported scienti fi c methods of analyzing
dioxins and furans once the sample is taken are reported including US EPA methods 1613,
8280, and
8290, most of which use high resolution gas chromatography/high resolution mass spectrometry
as a detection tool.
2 In order to understand the possibility of removal of PCDDs/Fs from
the environment photodegradation strategies have been evaluated. For the photodegradation,
heat activated persulfate (HAP), hydroxyl radical source, metal-based materials including: TiO 2, SnO
2, Silver doped zeolites, gold doped zeolites have proven capable of degrading dioxins and furans
in short period of time.
3 Dioxins and Furans, as well as other POPs have been studied and
reported in major industrial countries such as USA, Canada, Europe, China, Japan and the
Middle East. Major fi ndings from these eras are discussed herein and summarized as follows:
a Data on the sources of PCDD/Fs in the environment indicate that
10
Trends in Environmental Analytical Chemistry 17 (2018) 1–13
in the USA the greatest emissions of dioxins were released from electricity and heat
generating plants, whereas in Canada, burning of household garbage has been identi fi ed as
the largest source of dioxin emissions.
b In the European Union, the highest emissions are reported in
France, Italy and Spain, mainly due to waste incineration and countries like Turkey, mainly
showed e ff ects on the food chain due to aquatic pollution from industrial discharges. c In
China, emission of dioxin from power generation and heat
supply, waste incineration, mining, and transportation accounted to a total of about 10,237 g
TEQ, moreover, rivers have a high level of pollution. In the case of Japan, the high industrial
activity in these regions, directly correlates with the high amounts of dioxins and furans
substances in the samples. d The Middle Eastern data showed that PBDE concentrations
were
generally higher at the urban sites when compared to the concentrations at remote sites.
Concentrations from open-burn municipal land fi ll in Jordan showed high total concentrations of
PCDD/PCDF. Food studies in Kuwait and Egypt, showed that some concentrations were lower
than permissible levels, while others, exceeded accepted concentrations. 4 Finally, in the
Middle East, one of the major problems with the
management of chemicals is the lack of readily available information on their hazardous
characteristics. Lack of studies targeting the concentrations and sources of emissions of POPs
derivatives indicating the need for further studies in the region.
Acknowledgement
We thank the Research o ffi ce at the American University of Sharjah for their Support.
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