Aire 1

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

journal homepage: www.elsevier.com/locate/treac
Dioxins and furans: A review from chemical and environmental perspectives T

⁎
Sofian Kanan , Fatin Samara
American University of Sharjah, Department of Biology Chemistry and Environmental Sciences, P.O. BOX 26666, Sharjah, United Arab Emirates
A R T I C L E I N F O A B S T R A C T
Keywords: Persistent organic pollutants (POPs) in the environment have generated great interest within the scientific
PCDDs community due to their toxic effect to animal, human health, and the environment. This review encompasses the
PCDFs historical presence of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in the world-wide
Sources environment. Information on exposure indicated that the main route of exposure of dioxins/furans to humans is
Worldwide environment
through ingestion, which is discussed in this paper. In addition, we present a thorough assessment of sampling,
GC/MS
Photocatalysis
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) preferred as a detection tool. Moreover, a detailed compi-
lation 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 conflicts in the region.
1. Background 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
Persistent organic pollutants (POPs) are harmful organic com- quantity of POPs contamination and it’s unfolding through organic
pounds that are resistant to biological, chemical, and photolytic de- phenomenon. The data obtained for the concentration of POPs in the
gradation. They are persistent in the environment especially in soils, food chain, is necessary to support the implementation of policies and
sediments, and air for several decades [1]. Because of their toxicity and processes to reduce the amounts of POPs within these chains [9,10].
persistency, they pose a significant threat to animal, human health, and The Stockholm treaty on POPs was instituted to control the con-
the environment since they accumulate in the fatty tissues of humans centration levels of POPs within the general population, as a result, “the
and animals [2,3]. In humans, POPs have been linked with behavioral, dirty dozen” was created. In specific, 12 different types of POPs in-
reproductive, developmental, endocrine, neurologic, and immunologic cluding aldrin, chlordane, dieldrin, endrin, heptachlor, hexa-
adverse health effects [4,5]. While in animals, they have caused dis- chlorobenzene, mirex, toxaphene, dichlorodiphenyl Trichloroethane
eases and abnormalities in a number of wildlife species including cer- (DDT), polychlorinated biphenyls, polychlorinated dibenzodioxins
tain kinds of birds, fish, and mammals. They are a global concern due to (PCDDs), and polychlorinated dibenzofurans (PCDFs), were identified
their transportation over long distances from the point of production or in order to be eliminated and controlled by 150 countries [11].
release since they can evaporate from the soils and travel through the PCDDs and PCDFs are generally classified as toxic and carcinogenic
air and condense in colder regions. unintentional by-products that are present in small amounts in the
According to researchers POPs are just a subset of more dangerous environment. The major issue with PCDDs/Fs is their extreme persis-
materials such as persistent, bio accumulative and toxic ((PBT)) che- tency in the environment, which is toxic to living organisms and can
micals including pesticides and organic compounds such as γ-hexa- potentially cause cancer. There are three main categories for dioxins
chlorocyclohexane, 1,1,1-trichloro-2,2-diethane, polychlorinated bi- and furans: polychlorinated dibenzo-p-dioxins (PCDDs), poly-
phenyls, polycyclic aromatic hydrocarbons (PAHs), polychlorinated chlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated bi-
naphthalene, polychlorinated dibenzo-p-dioxins (PCDDs), poly- phenyls (DL-PCBs). PCDDs and PCDFs are released as byproducts of
chlorinated dibenzofurans (PCDFs), as well as groups of brominated anthropogenic activities, or processes such as forest fires [12]. They are
flame retardants such as polybrominated biphenyls (PBBs) [6,7]. The byproducts of the synthesis or combustion of chlorine based compounds
quantity of the POPs in the atmosphere increases due to the massive 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 Trends in Environmental Analytical Chemistry 17 (2018) 1–13
compounds include 210 possible congeners and at least seventeen have a total of 198 g TEQ/year according to the 1997 national inventory
been identify as toxic with wide ranging toxicity from which 2,3,7,8- [24]. Steel manufacturing and iron sintering processes were found to be
tetrachlorodibenzo-p-dioxin (TCDD), was identified as the most toxic among the major sources of dioxins and furans emissions despite the
compound [1,13]. Humans are normally exposed to dioxins and furans fact that low levels of chloride may enter the combustion processes. In
through contaminated food products which are often affected through addition, extensive studies on municipal solid waste, medical waste,
the accumulation of these chemicals in the food chain and in high fat sewage sludge, and hazardous waste incinerations showed that low
foods, such as eggs, dairy products, animal fats, and fish [11,14–19]. In levels of dioxins emissions, can be achieved from even trace quantities
order to obtain the toxicity of these compounds in vivo and in vitro data of organic and inorganic chlorides. An example of this common source,
involving processes such as uptake, tissue distribution, metabolism, is the municipal solid waste in Canada, containing seven solid waste
receptor binding, and activation was obtained in relative to the most treatment facilities having a capacity of 25 t/day and they handled 3%
toxic congener 2,3,7,8-TCDD. To express concentrations of the most of the [25,26].
toxic PCDDs/Fs and dioxin-like PCBS in relation to their toxicity toxic Waste incineration is responsible for 37.6% of the total dioxin
equivalency factors (TEFs) have been used and determined by the emissions from anthropogenic sources with a 74.5 g TEQ/year [2,24].
comparison of its toxic or biological endpoints to those of the 2,3,7,8- Moreover, it was reported that wood can absorb significant amounts of
TCDD. TEFs for 17 PCDD/F congeners are then used to estimate the sodium chloride when stored in the marine waters along the west coasts
overall dioxin-like toxic equivalency (TEQ) found in samples, with of Canada. Under certain combustion conditions, the burning of salt
2,3,7,8-TCDD having a reference TEF of unity. TEFs are used as a laden wood waste in pulp mill power boilers leads to the formation and
consistent method to report the toxicities of varying mixtures of dioxin- emission of dioxins and furans. The formation of these compounds is
like compounds. They have been developed to facilitate comparative favored under poor combustion conditions as the gas phase precursors
risk assessment and regulatory control of exposure to these mixtures formation such as chlorophenols and polycyclic aromatic hydrocarbons
[20–22]. will be favored [26,27]. Thus, dioxins and furans can be formed
The goal of this review article is to access the current status of the through adsorption/desorption on ash particles. A total of 7.9 g TEQ/
analysis of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated year of dioxins and furans emissions were resulting from coastal power
dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (DL- boilers burning salt-laden hog fuel which is equivalent to 4% of the
PCBs) in the global environment using some of the main countries as total anthropogenic emissions [24]. These emissions are regulated ac-
examples. In addition, we will briefly explore and discuss the most cording to Canada wide-standards to be reduced, in 2006, to 0.5 ng
common techniques for the extraction, clean-up and instrumental de- TEQ/m3 for existing reboilers and 0.1 ng TEQ/m3 for new reboilers
termination of this compounds in different matrixes, as well as the [28]. Other main sources around the world will be discussed in section
common techniques for their removal and/or degradation. For simpli- 3 of this paper.
city purposes, PCDDs, PCDFs and DL-PCBs will be often referred as Finally, dioxins are also formed in pulp and paper mills effluent
dioxins throughout the paper. discharge as a result chlorine bleaching. Since the emissions of dioxins
and furans from pulp and paper mills is under the legal limit of quan-
tifications, a total emission of 2 g TEQ/year has resulted from all pulp
2. Common sources of PCDDs, PCDFs and DL-PCBs 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
Studies have shown that concentrations of dioxins and furans were attributed to food consumption, hence, creating various adverse health
low in the early 1900s, and showed signs of increase during the 1920s effects in human and animals. Dioxins vary in their toxicity that de-
to the 1970s [18,23]. This indicates that they are mainly formed due to pends mainly on the type of dioxin, frequency and duration of the ex-
anthropogenic sources, as summarized in Fig. 1. In specific, any process posure [3,24,29,30]. Pentachlorophenol (from the textile industry) has
involving organic chlorine or inorganic chlorides presents a significant been suggested as the major source of PCDD/F in sewage sludge. For
source of dioxins and furans. Conical municipal waste combustion in this reason, countries such as Germany, banned the use of the chemical
new found land, waste incineration, coastal pulp mill boilers burning resulting in a significant reduction of PCDD/F levels in sewage sludge
salt laden wood, residential wood combustion, iron sintering and [31].
electrical arc furnace steel manufacturing are the major sources of di-
oxins emissions as generate 80% of the total national emissions that had
Fig. 1. Major Dioxins Sources in the Environment.
2
3. Most common methods for analysis and detection MS) provide excellent sensitivity and linearity [47–50]. In the case of
low-resolution GC/MS two mass-selected congeners from the molecular
3.1. Extraction and clean-up techniques cluster were monitored in a single ion monitoring (SIM). Congeners are
identified based on isotopic ratio and retention time in both techniques.
Various extraction and determination methods of dioxins and di- In 2000 the European Union (EU) was pushed to start an efficient
oxin- like compounds from different matrices have been reported monitoring program to ensure the proper quality of European food and
[32–35]. For example, Suzuki et al. suggested the use of solvent ex- feed. As a result, the European Commission (EC) began to propose
traction for soil and dust samples with large solids, such as pebbles and legislation to regulate Maximum Residual Levels (MLs) for PCDDs,
twigs, which must be removed manually. Next, the soil samples are PCDFs and DL-PCBs in food stuffs and feed products, as well as
placed in a sieve and shaken to eliminate larger particulate matter then guidelines for analytical methods to support and implement continuous
mixed with a 1:1 mixture of acetone and hexadecane with the resulting monitoring of food and feed. A new regulation was issued in 2006
mixture being filtered and stored in a cold storage until analysis is done (2006/794/EC) where a random monitoring of the presence of dioxins,
[33]. In contrast, for extraction of dioxins from air samples, Li et al. dioxin-like PCBs and non-dioxin-like PCBs, by Member States on the
suggested passing the sample through a 1:1 mixture of hexadecane and basis of criteria defined by Commission Recommendations 2004/704/
dichloromethane. In order to eliminate any undissolved particulate EC and 2004/705/EC for feed and food, respectively [51,52]. The ac-
matter, the resulting solution was passed through a multilayer silica gel cepted specific limit of quantification (LOQ) of an individual congener
column and then through an activated carbon column. The adsorbed is the concentration of an analyte in the extract of a sample which
dioxins can then be eluted using dichloromethane-hexadecane mixture produces an instrumental response at two different ions to be monitored
with all samples are stored in cold prior their analysis [34]. In water with an S/N (signal/noise) ratio of 3:1 for the less sensitive signal and
samples, Gao et al. proposed filtering and passing the water samples fulfilment of the basic requirements [51,52]. Recommendation 2006/
through a column containing a hydrophobic resin, such as XAD-2, that 794/EC suggests to adopt picogram/g (pg/g) when reporting results for
traps dissolved dioxins. After drying, a 1:1 solution of dichloromethane dioxins, furans and dioxin-like PCBs, and nanogram/g for the non-di-
and hexadecane elutes the dioxins with the final solution being col- oxin-like PCBs. The Scientific Panel on Contaminants in the Food Chain
lected and stored in cold temperature prior the analysis [35]. In the case of the European Food Safety Authority (CONTAM Panel of EFSA), re-
of sludge samples, sludge extracts are transferred to hexane and acid- lated to the presence of NDL-PCBs in feed and food, noticed that the
treated with concentrated sulfuric acid. Furthermore, after evaporation, sum of the six indicator PCBs represented about 50% of the total Non-
extracts are scrubbed in a multi-layered silica gel column, followed by a dioxin like PCBs in food [52]. Recently, the European Regulations
basic alumina column, and finally through a PX-21 active carbon laying down methods of sampling and analysis for the EU official
column [36,37]. control of levels of PCDDs/Fs in food and feed have been recently
Analysis of dioxins contaminated in soil is very critical, hence, ad- amended by EU (Regulation Nos. 589/2014 and 709/2014) with a
vanced soil mineralogy methods have to be used in this process. In major update is the recognition of gas chromatography (GC) triple
specific, the extraction of the dioxins can be done through various quadrupole mass spectrometry (GC–QQQMS/MS) as a confirmatory
methods such as pressurized liquid extraction strategy with sulfuric tool for checking compliance with maximum levels (ML) [53]. These
acid-impregnated silica is used for the extractions of the compounds revisions have been initiated since this technology now exhibits similar
[38]. The absorbance arising is inversely proportional to the amount of performances to GC (magnetic sector) high resolution mass spectro-
dioxins, from which success from this technique becomes operational metry (GC-HRMS) [53]. Other methods including gas chromatography-
[39]. This method requires calculation of the toxicity equivalence of the time of flight mass spectrometry (GC x GC TOFMs) [54–57] and gas
test by the provisions of the U.S environmental protection agency re- chromatography Fourier Transform Ion Cyclortron Resonance Mass
port [40]. Rapid extraction technique has an extraction efficiency of Spectrometry (GC-FTICRMS) have been used and developed
approximately 81%. This automatically gives an indication that it is [48,49,58].
possible to extract dioxins following the possibility of omitting air Other studies have tested methods not commonly used and obtained
drying step [12,41–43]. positive results. For example, a Canadian studies, have noted that better
Other reported methods exist for blood plasma and animal tissues sensitivity is obtained when applying a gas chromatograph-tandem
where the extraction and clean-up is performed in several steps in- quadrupole-Fourier transform ion cyclotron resonance mass spectro-
cluding an initial extraction with a C18 bonded silica cartridge, fol- meter (GC–MS/MS-FTICRMS). This method is used to investigate
lowed by clean-up with a dual-cartridge composed of bonded benze- chlorinated-dioxins/furans (CDDs/CDFs) as well as mixed halogenated
nesulfonic acid cartridge in series with a silica cartridge, and a final step dioxins/furans (HDDs/HDFs) at 50,000–100,000 of a resolving power
incorporating a florisil cartridge [44]. Moreover, other studies have on the capillary gas chromatographic time [59]. Another study per-
reported analysis of milk using Soxhlet-extracted and then cleaned up formed in the United States computed the emission index using the EPA
using Power-Prep system automatically and/or the use of gel permea- database and the annual emission was reported in ng TEQ/Yr using a
tion chromatography, alumina clean-up and porous graphitized carbon HRGC/HRMS operated in positive electron ionization mode with a mass
chromatography [45,46]. In general, based on the matrix the extraction resolution above 10, 000 following the guidelines set by the EPA [60].
and clean up procedures will vary. In addition, an interesting publication, reported on the quantitative
measurements of dioxins and furans by only using infrared absorption
3.2. Quantification and detection techniques laser spectroscopy was presented in a direct absorption mode, making it
the first study to report on the potential use of IR spectroscopy [61].
Traditionally, toxicity levels of PCDDs/Fs have been determined by Due to their widespread presence in the environment, PCDDs and
gas chromatography/high resolution mass spectrometry (HRGC/ PCDFs have become routinely measured by the environmental agencies
HRMS) analysis for congener concentrations and reported as TEQs. The of several countries around the world. Several methods have been re-
total TEQ of a mixture is the sum of the TEF of each individual congener ported by the United States Environmental Protection Agency (USEPA)
times its concentration. Some common parameters for the GC/MS for analyzing dioxins and furans in environmental compartments as
analysis include the injection temperature at 300 °C with the column shown in Table 1. According to Harrad, there are other numerous
temperature being ramped from 120 to 330 °C [34,35]. Identification of methods that can be used to analyze samples for dioxins and furans
PCDDs/Fs is typically achieved by isotopic dilution, where at least two under various conditions [27]. For instance, USEPA Method 8280 is the
ions per congener could be identified. Techniques incorporating gas most appropriate method used for detecting trace amount of dioxins in
chromatography coupled to Tandem Mass Spectrometry (GC-QITMS/ air. Wittich reaffirms that the nature of the sample determines the most
3
Table 1
United States Environmental Protection Agency (USEPA) for analyzing dioxins and furans in environmental compartments.
Method Compounds of Interest Environmental Matrix Analytical Tool References
USEPA Method tetra- through octa-chlorinated dibezo-furans (CDFs) and dibenzo-p-dioxins sediment, water, sludge, tissue, soil HRMS/HRGC [63–65]
1613 (CDDs)
USEPA Method 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD), 2,3,7,8- water, soil, fly ash, and chemical waste HRGC/LRMS [27,66]
8280 tetrachlorodibenzofuran (2,3,7,8-TCDF), and the 2,3,7,8-substituted penta-, samples, including stillbottom, fuel oil, and
hexa-, hepta-, and octachlorinated dibenzo- p-dioxins(PCDDs) and sludge matrices
dibenzofurans (PCDFs)
USEPA Method tetra- through octachlorinated homologues; PCDDs), and polychlorinated variety of environmental matrices HRGC/HRMS [67,68]
8290 dibenzofurans (tetra- through octachlorinated homologues; PCDFs)
Method 23 and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/PCDFs), ambient air including stack gas emissions, fly HRGC/HRMS [69]
TO-9 polybrominated dibenzo-p-dioxins and dibenzofurans (PBDDs/PBDFs), and ash, soil, sediments, water, and fish and
bromo/chloro dibenzo-p-dioxins and dibenzofurans (BCDDs/BCDFs) human tissue
appropriate method that can be used. Sludge, liquid, air, and soil doped zeolites [89] are well studied in literature. Since the presence of
samples work best in different methods based on their physical nature the hydroxyl radicals (OH) are expected to be an important removal
[62]. However, they have a conventional method of presenting their pathway of polychlorinated dibenzo-p-dioxins and dibenzofurans
findings in a way that is easy to understand after an interpretation of (PCDD/F) in the atmosphere, Wu et al. have developed a system to
the results has been made. measure the rate constants of the gas-phase reactions of OH with semi-
volatile organic compounds using on-line mass spectrometry. OH re-
4. Photocatalysis and/or removal techniques in environmental action rate constants were determined in helium for 1,2,3,4-tetra-
compartments chlorodibenzo-pdioxin at 373–432 K using a heated quartz reaction
chamber [76]. For example, under 254 nm UV source, photolysis of O3
Several photocatalysis studies have been explored in order to reduce in the presence of H2O and the photolysis of H2O2 served as OH sources.
dioxins and furans in the environment. Kostantinov et al. used a low- The reaction rate constant of 1,2,3,4- tetrachlorodibenzo-p-dioxin with
pressure ultraviolet mercury lamp to destroy dioxin-like compounds, OH was 8.5 × 10−13cm3 s−1 at 298 K [74,75]. The effect of the OH
both as individual congeners and in actual waste analytical samples. radical on the photodegradation of various chlorinated dioxin is illu-
Experiments with 1,6-[3H]-2,3,7,8-TCDD revealed that the principal strated in Fig. 2 [88] with the rate constants for different catalyzed
photolytic pathway involves cleavage of CeO bonds rather than CeCl systems are summarized in Table 2.
bonds, giving chlorinated hydroxydiphenyl ethers as the initial pro- Wu et al. have reported the direct photolysis and photocatalytic
ducts. The photolysis products from 2,3,7,8-TCDD do not bind to either processes for 2,3,7,8-TCDD and 1,2,3,6,7,8-HxCDD under TiO2, ZnO,
the rat hepatic Ah receptor or the estrogen receptor in vitro, making it and SnO2 catalysts. SnO2 showed low activity because the UV light
unlikely that the products from the UV treatment of PCDD/PCDF in energy was partial to excite SnO2 in a single catalyst system. In this
laboratory waste will show either Ah or estrogen receptor-mediated case, SnO2 performed as an appropriate photogenerated-electron sca-
toxicological effects [70]. venger in coupled catalyst systems [78]. TiO2 film under irradiation
The photolytic activities of dibenzo-p-dioxins and −furans in me- with 365 nm UV was used for these experiments and the compounds
thanol and n-hexane were found to follow first order decay rates. The were immobilized on TiO2/solid phase. No 2,3,7,8-substituted PCDD/Fs
photolysis rate constants in n-hexane increased with increasing number products were detected in photocatalytic process under the experi-
of halogen atoms in the PCDD and PCDF framework. For example, the mental conditions. The reaction rate constants were 0.3256 h−1 for
monobrominated and the octabrominated derivatives showed rate 2,3,7,8-TCDD (2000 ng) in UV/TiO2 reaction, 0.2474 h−1 for
constants of 4.5 × 10−4 s−1 and 7.7 × 10−3 s−1, respectively. In ad- 1,2,3,6,7,8-HxCDD (2000 ng) in UV/TiO2 reaction, and 0.0666 h−1 for
dition, the dibrominated derivative shows a rate constant of 1,2,3,6,7,8-HxCDD (50 ng) under direct UV Irradiation [76,77].
4.0 × 10−3 s−1 while the heptabrominated furan has a rate constant of Moreover, silver modified zeolite Y has proven capable of degrading
8.3 × 10−2 s−1. Photolysis in methanol is nearly six times slower than 2,3,7,8-TCDD, the most toxic PCDD/F derivative, in a methanol/THF
in n-hexane and the bromine compounds were identified to react by an solution [95,96]. The presence of silver loaded on the zeolite decom-
order of magnitude faster than the chlorine analogues [71]. poses 2,3,7,8-TCDD by 86% after 254 nm UV irradiation for 6 h. This is
It was found that pure water or 60% acetonitrile/water solutions of a noticeable increase over UV irradiation alone which reduce the TCDD
2, 7-DCDD and 1, 2, 7, 8-TCDD were photodegraded faster at 300 nm concentration by 28% within the same time frame. The silver Y cata-
than their PCDF analogues. PCDD compounds have higher photo- lysts also lead to a decrease in the emission band intensity since the
degradation rates in acetonitrile/water than in pure water. For ex- 2,3,7,8-TCDF absorbed on the catalyst’s surface. The amount of the
ample, the photodegradation rate constants for individual PCDDs and adsorbed 2,3,7,8-TCDF on the different AgY catalysts reached to
PCDFs varied from 8.9 × 10−2 min−1 for DCDD in pure water to 18.9–37.9% of its initial concentration respectively. ELISA showed that
1.0 × 10−3 min−1 for OCDD in 60% acetonitrile water. Lower chlori- in contrast to the rest of the samples, the OD of the TCDF and TCDD
nated PCDDs and PCDFs accounted for less than 18% of the loss of the samples irradiated with 254 nm in the presence of AgY2 catalyst was
parent compounds [72,73]. Kim et al., have found that PCDD/Fs on high at 40 min suggesting a decrease in toxicity of the degradation
particulate can be treated by heat activated persulfate (HAP) where the products [95,96]. Isosaari et al. have investigated the effect of olive oil
removal rates of PCDD/Fs was found to decrease as the numbers of on the photodegradation PCDD/Fs in contaminated sawmill soil.
chlorines increased by HAP. In addition, PCDD/Fs on the fine particle 2,3,7,8-TCDD was reduced in concentration by 59% and the WHO-TEQ
were removed better than on the coarse particle with more persulfate in contaminated sawmill soil was reduced by 48% after blending the
being consumed to remove high chlorinated compounds [72]. soil with two doses (20 + 20%) of olive oil and exposure to sunlight for
Several catalysts such hydroxyl radical source [74,75], metal based four weeks [71].
materials were identified to be active catalysts for the photodegradation The first report of the degradation of highly chlorinated PCDDs and
of organic pollutants especially polyaromatic hydrocarbon and pesti- PCDFs by a microorganism was performed by Takada et al. using white
cides. Materials including TiO2 [76,77], ZnO [76,77], SnO2 [78], Silver rot fungi. Degradation of a mixture of 10 derivatives of tetra- to octa
doped zeolites [79–85], gold doped zeolites [86–88], and mixed metals CDDs and CDFs by the white rot fungus Phanerochaete sordida YK-624
4
Fig. 2. Pathways of OH radical addition on HpCDD and OCDD to form a

hydroxycyclohexadienyl radical [90].
Various studies have indicated that PCDD/F compounds are sub-

Table 2
jected to biodegradation in the environment as part of the natural
A summary of experimentally determined rate constants of individual PCDD congeners
under different conditions.
chlorine cycle where lower chlorinated dioxins can be degraded by
aerobic bacteria at high percentages. In his article, Field et al. provided
Studied derivative System/catalyst Rate constant k (h−1) References an extensive review of the work done for the degradation of various
chlorinated dioxins and furans under different microorganisms [98].
1, 2, 3, 6, 7, 8-HxCDD UV 0.07 [77]
UV 0.06 [76]
The overall pathway shown in Fig. 3 involves cycles of oxidation by
Sunlight 0.01 [91] Lignin Peroxidase (LigP) and/or Manganese Peroxidase (MnP) forming
UV/ZnO 3.28 [76] quinones, followed by reduction to hydroquinones or catechols and
UV/SnO2 3.19 [76] subsequent methylations to methoxybenzenes. 124 THB is subject to
UV/ZnO-SnO2 7.47 [78]
ring cleavage, which could lead to mineralization to CO2 [98].
UV/TiO2 Very fast [76]
OCDD UV 0.06 [73]

UV 0.17 [92] 5. PCDDs and PCDFs in the environment from various countries
UV 0.01 [92]
UV 1.00 [94]
To assess the current situation of the presence of PCDDs, PCDFs and
Sunlight < 0.01 [91]
Sunlight 0.16 [92] DL-PCBs in the global environment, selected studies from various
UV/ZnO 0.74 [76] countries were included in this study. The studies include the main
UV/SnO2 0.28 [76] sources and the current concentrations found in those specific studies in
UV/ZnO-SnO2 1.41 [78] industrialized countries such as United States, Canada, Europe, China,
UV/TiO2 0.12 [90]
Japan and the Middle East. Although, vast literature is available for
UV/TiO2 5.30 [76]
O3 0.37 [94] most countries, only selected studies are discussed below.
UV/O3 1.09 [94]
UV/H2O2 0.04 [93]
5.1. Dioxin studies in the United States
2,3,7,8-TCDD UV 0.09 [93]
Sunlight 0.04 [92]
Due to their formation as unintentional by-products and persistency;
1,2,3,4,7,8-HxCDD UV 0.01 [93]
PCDDs, PCDFs and DL-PCBs are still present in considerable amounts in
UV 0.18 [92]
Sunlight 0.10 [92] the environment. For instance, in 2011 air analysis showed that the
concentrations of dioxins were the highest during that time that has
ever been reported in history [11]. In an effort to determine the amount
of dioxins in the atmosphere, the EPA has implemented a system known
was studied in a stationary low-nitrogen medium. The results suggest as the National Dioxin Air Monitoring Network (NDAMN). The system
that white rot fungus is able to degrade both PCDDs and PCDFs with was operated starting 1998 until 2004, where over 600 samples were
percent degradation values of approximately 40 (TCDD) to 76% collected and analyzed [99].
(HxCDD) and 45 (TCDF) to 70 (HxCDF), respectively [97]. In addition, in order to compute a dioxin emission index, 40
5
toxic equivalence factor (TEFs) assigned by the World Health

Organization (WHO), ranging over an order of magnitude between low
and storm flow conditions (0.226–6.26 ng/L) with the flow of dioxins
and furans during storm is reported to be 6.26 m3/s during storm flow
and 0.226 m3/s during low flow, 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 fish contamina-
tion in the Tittabawassee River floodplain 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 po-
pulation. 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,
fish 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 different industrial facilities as well as 127 wastewater treat-
ment 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 identified by the Michigan De-
partment of Public Health. Twelve different fishes from the Tittaba-
wassee and Saginaw Rivers were measured for their concentrations of
PCDD/Fs and PCBs, in which resulted in different concentrations as the
lipid content in each fish varied from one species to another. In specific,
the carp fish received the highest ΣPCDD/Fs and ΣTEQs compared to
other species (i.e. ΣTEQs = 54 ± 59 pg/g ww). Next, followed the
channel catfish and the northern pike with a ΣTEQs value of
(34 ± 28 pg/g ww) and (13 ± 11 pg/g ww), respectively [102]. The
least concentrations of ΣTEQs were found in bluegill with a ΣTEQs
value of (1.7 ± 1.5 pg/g ww) [102].
The emissions of dioxins from various sources such as waste in-
cineration 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
Fig. 3. Proposed pathway of 2,7-dichlorodibenzo-p-dioxin (2,7-DCDD) degradation by heat generation have increased from 70 g TEQ/year in 1987 to 118 g
the white-rot fungus, phanerochaete chrysosporium [98]. 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
different participates from various locations in the US were inter- concentrations in water and marine environments is important, because
viewed. The emission index was computed using the EPA database. The dioxins can be taken up by plants and fish and could later biomagnified
different samples collected from houses included several vacuum bags to humans [103]. As dioxins are hydrophobic, these compounds are
that were frozen at −20 °C until analysis [60]. Moreover, Henri H. adsorbed on particulate matter in aquatic settings, resulting in very low
Dwyer, examined the release of dioxins from controlled industrial and concentrations in dissolved phases, in the nanometer or picometer per
open burning sources. These sources were later classified into: waste liter range. Single phase samplers can also be used, consisting of low
incineration, waste to energy, electricity and heat generation, me- density polyethylene (LPDE) strip and silicone rubber, as they involve
tallurgical processes, as well as non-controlled smaller scale combustion easier sample processing. Lastly, the continuous integrative flow sam-
processes for open burning. The results stated that the greatest emis- pler (CFIS) is a newly designed sampler, involving the use of a pump,
sions of dioxins were released from electricity and heat generating powered by batteries that can be fully submersed, with sampling rates
plants, which contributed a total of 66.2% of these emissions, followed that remain unaffected by water turbulence or velocity [104]. Using
by metallurgic processes, waste incineration and the WTE industry. such methods, the concentrations of dioxins in water could be mea-
Open burning sources contributed 7.2% of the emissions, with landfill sured.
fires contributing the most by 44% followed by forest fires at 28%
[100]. In contrast, for the open source emissions of dioxins, the values 5.2. Dioxin studies in Canada
reported showed an increase of 43%. This is mainly due to the various
large forest fires and landfills that account for about 77% of the major Burning of household garbage has been identified as the largest
open source emissions and a 93% increase of the emissions. This in- source of dioxin emissions in Ontario where open burning of agri-
crease is due to the higher temperatures in forest fires and better re- cultural plastics is one of the main contributors [105]. Burning 10,000
porting of the landfill and forest fires [100]. pounds of agricultural plastic has the potential to contaminate
Gilbreath and McKee conducted a research on urban watersheds in 75,000 kg of soil from exposure to dioxins, based on Canadian Soil
San Francisco to determine the concentration of chemicals such as di- Quality Guidelines. In Alberta alone, it is estimated that more than 20
oxins, organochlorine pesticides, and pyrethroids. The analyzed sam- million pounds of agricultural plastics are sold annually, and that the
ples, confirmed the presence of seven types of dioxins which have a predominant method of waste management is open burning. If half of
6
this plastic is handled through on-site burning, it has the potential to contamination for sea fish and freshwater fish and 55–75% for other
contaminate 75 million kg of soil due to dioxins exposure [105]. The fish products. Reported concentrations of PCDD/F and DL-PCB in Ve-
contamination of soil has its pathways for human by the consumption getable products did not exceed 0.01 pg WHO-TEQ g−1 fresh weights
within a food web such as vegetation to grazing animals to humans. [112]. Moreover, in Netherlands, the average concentration of dioxins
According to a comprehensive risk assessment study for human and and DL-PCBs in fish was found to be higher than in meat products.
ecological risk that was undertaken at a site in southern Ontario, the Results show that the levels of PCDDs and PCDFs in most vegetable
average soil for the most toxic dioxin, TCDD, is 11.1 pg/g DW [106]. products are close to or lower than low-fat animal products such as beef
Discharges of dioxins and furans to the Canadian aquatic environ- [113]. The distribution of compound in soil is more heterogeneous than
ment reached non-measurable levels in 1995 which made the point in air which causes difference concentration in samples [113].
source discharges to water to be the target of the Canadian federal and France is known to be the biggest emitter of dioxins in Europe since
provincial regulation, as well as industry innovation to change they lack regulations regarding PCDD/F emissions form waste in-
[107,108]. As a result, many studies were made in Canada to determine cinerators in plants (same with Italy and Spain) [114,115]. As of 2005,
the concentrations of dioxins and furans in its contaminated water. One most of the industrial processes in Germany were required, by law, to
of these studies was conducted to test the water contamination of the reduce emissions of dioxins from 400 g to less than 0.5 g in air, and
Great Lakes by testing the lake trout because of its presence across all have an emission limit of 0.1 ng I-TEQ/m3 [34,115,116]. Moreover, it
Great Lakes and high lipid content which makes it suitable for mon- was found that the introduction of waste incineration actually reduced
itoring levels of organic contaminants [23]. The lake trout was frozen the potential excretion of dioxins that would have otherwise been
and tested through a specific analysis and then the amount of PCDDs produced naturally from forest fires due to extensive filter units that
and PCDFs were determined in terms of TEQs. The study showed that prevent the release of high metal content chemicals.
the highest TEQs were observed in Lake Ontario Lake trout with values Another good matrix to study is ‘street dust’ which refers to the
ranging from 22 to 54 pg/g [23]. However, the temporal data from deposited dust on paved surfaces at industrial sites and next to roads
1989 to 1999 depict a promising scenario suggesting that TEQs in Lake [33]. Although limited data is published a distinctive trend was found
Ontario Lake trout are decreasing annually at approximately 1.5 pg/g in West North Rhine-Westphalia, Germany, relating particle sizes of the
[23]. This high contamination amount in lake trout shows that the dust and increasing concentrations of PCBs and PCDD/Fs in street dusts
water of Great lakes is also significantly affected by these compounds. [117]. Water is also an important matrix to study when investigating
The concentration of PCDDs/PCDFs in poultry samples in Canada was the contamination of dioxins and furans. Although poorly soluble in
2.6 pg I-TEQ/g [109]. Lastly, a study was made in Canada to account water, some of these low concentrations can still exist in drinking and
for the PCDDs and PCDFs concentrations (pg I-TEQ/g fat) in human surface waters [35]. Most of the releases from the incineration and
milk and showed that the concentration in years 1986–1987 was 15 pg waste sites can easily contaminate the water exerted back into the en-
I-TEQ/g fat [109]. vironment, causing bioconcentration and eventually biomagnification
Atmospheric transport is a primary pathway for the transfer of in the food chains. The Baltic Sea is known to be one of the largest
PCDDs and PCDFs to terrestrial and aquatic ecosystems via deposition rivers in Central Europe, which unfortunately, is one of the areas most
which makes it essential for the Canadian government to test the am- contaminated by POPs including PCDD/Fs. Because of the possibility of
bient air for the contamination of these compounds in air. In 1981, the high toxic exposures, it is forbidden to use the fish obtained from this
Canadian tested ambient air had a range of dioxins and furans con- region for human consumption [118]. In Germany, the river Elbe was
tamination in a range of 0.4–36.7 pg/m3 [110]. This range was due to also found to entail high levels of PCDD/Fs based on sampling con-
taking samples from different locations over the country, where in- ducted on eels and whitefish. Usually, the highest sources of dioxins
dustrial areas had a higher amount of dioxins and furans than other and furans that are released to land in Europe come from pesticide
areas. production, accidental fires and again, incineration of Municipal Solid
Wastes (MSW) [115].
5.3. Dioxin studies in Europe Comparative sample results from Germany, France, and Netherlands
were investigated to determine concentration levels of dioxins and
Analysis of dioxin/furans and dioxin-like PCBs (DL-PCBs) were furans that are found in street dust, raw cow milk, home produced eggs,
performed in Germany in accordance to the requirements of respectively. Table 3 summarizes the results obtained where street dust
Commission Regulation methods of sampling and analysis for the offi- is observed to have the highest concentration of PCDD/PCDFs. How-
cial control of levels of DL-PCBs in certain foodstuffs including sheep ever, when food products were compared, home produced eggs had a
[111]. Results show that 72 out of 77 investigated sheep liver samples much higher concentration than raw cow milk, which might be due to
exceeded the European maximum tolerance level of 6.0 pg WHO- fat content.
PCDD/F-TEQ g−1 fat with 71 samples also exceeded the cumulative In Greece, a country where industrial emission sources are very
maximum tolerance level of 12.0 pg WHO-PCDD/F-PCB-TEQ g−1 fat set limited, the most important source of PCDDs/Fs is considered to be the
in the EU for the sum of PCDD/PCDFs and DL-PCBs in livers of sheep uncontrolled combustion of municipal solid waste in open landfills.
and derived products. Results show no significant correlation between PCDD/F and PCB contamination levels in blood and human milk from
the levels of PCDD/PCDFs or DL-PCBs and the fat content of the sam- Greece samples were low compared to the previously reported dioxin
ples. However, the highest concentrations where detected in female data from other European countries giving no indication of a particular
sheep livers, indicating that gender might play a role in the bioaccu- health risk. Furthermore, Athens had significantly higher total PCB
mulation of this POPs. In addition, no correlation was determined be- concentrations compared to the rural region of Kozan [120,121]. Sev-
tween their age and the burden of their livers with PCDD/PCDFs or DL- eral studies, have reported the presence of PCDD/Fs pollution in the
PCBs [111]. region. A study on the Rhone River, reported that it annually discharges
In France, food samples were monitored by the ‘Market Basket’ an average of 1040 m3/s downstream. Concentration measurements
which gathers data on almost all food products mostly of animal origin were detected using high resolution HRGC/HRMS for a total of 7 PCDDs
and some fruit, vegetables, and vegetable oils [112]. Results showed and 10 PCDFs [122]. Other studies have reported on the presence of
that in meat products 85% of the chemicals present are DL-PCBs. In dioxins and furans soil samples taken from a sawmill site in Sweden. In
dairy products and eggs, the proportion PCDD/F and DL-PCBs is better the site, chlorophenols (CPs) were being used during the 1950′s–1970′s,
balanced: 30:70 and 45:55%, respectively. Sea (wild and farmed) and where dipping was used for short term prevention of rot and blue
freshwater fish have a total concentration of between 2.7 and 2.9 pg staining of wood (newly sawn timber) [123]. The most common pre-
TEQ g−1 fresh weight where, DL-PCBs account for 80–85% of total servatives at that time were mixtures of chlorophenols which contained
7
Table 3
PCDDs/Fs concentrations detected in samples from European countries.
Sampling location Sampling Sampling Method Sampling Site/type No. of Samples dl-PCB PCDD/PCDF Ref.
Matrix TEQ [ng/ TEQ [ng/kg]
kg]
North Rhine- Street Dust Pressurized Liquid Extraction and Gas Rural ® 6 6.5 2.4 [117]
WestphaliaGermany Chromatography coupled to Mass Urban (U) 16 6.8 4.4 [117]
Spectrometry Industrially Influenced 19 6.4 3.6 [117]
Urban (UI)
France Raw Cow Milk Liquid-liquid Extraction and Gas 93 plants from 17 239 0.57 0.33 [119]
Chromatography coupled with High different dairy groups
Resolution Mass Spectrometry
Netherland Home Gas Chromatography and High Resolution 62 addresses from 20 eggs from each 2.0 2.8 [7]
Produced Eggs Mass Spectrometry various regions participant
PCDD/Fs produced during the manufacturing process of preservatives be concluded that the concentrations of dioxins and furans in the am-
[123]. Therefore, the most recent Swedish guidelines documented by bient air of China are comparable with the urban air of other countries
Henriksson et al., allocate a concentration of 20 ng/kg dw WHO-TEQ to like Athens (166.6–701.5 fg/m3) and Brazil (47–751 pg TEQ/m3)
classify the land used for habitation and a concentration between [130,131].
20 ng/kg dw WHO-TEQ and 200 ng/kg dw WHO-TEQ to classify land Reports suggest that 16.1% of China’s soil suffered from con-
used for industrial purposes [123]. tamination (BBC Report, 2016). One of the major soil contaminants in
In Turkey, PCDD/Fs and PCBs are typically disposed into the black China are dioxins and furans that are formed during industrial pro-
sea by industries, in addition to, contamination by countries sur- cesses and have the potential to become harmful to the human health
rounding the Black Sea. This increase in aquatic contamination has and environment [132]. A study using combustion technology reported
resulted in accumulation of harmful residues of PCDD/PCDFs and PCBs on the long-monitoring of dioxins and furans around medical waste
in the aquatic organism in the marine environment which directly af- incinerators in the North of Zhejiang, China. For this study, about 10 g
fects the food chain [124]. Four sea bass samples were studied, three of soil were collected on a dry basis, and extracted using Selective
sea bream samples and one imported fish feed sample used in one of the Pressured Liquid Extraction (SPLE). Since 2007, studies showed that the
sea bass farms. Persistent organohalogen compounds have a strong dioxin and furans concentrations increased throughout the years due to
tendency to accumulate in fat, which is why concentrations are usually of the increase of pesticides, solvents, hydrocarbons, and factory
normalized on a fat basis. Hence, the highest levels of PCDDs, PCDFs emissions [133,134].
and PCBs were observed in sea bream, as expected because of the During the last two decades, Pearl River Delta (PRD) has become
higher lipid content [124]. one of the most prosperous regions in China after undergoing a rapid
economic, industrial and agricultural growth. The population increased
5.4. Dioxin studies in China from 962 million in 1978 to 1314 million in 2006, which also resulted
in an increase in the demand of agricultural products. As a result, the
China is known to have several studies targeting the presence of total uses of chemical pesticides and fertilizers increased significantly
dioxins and furans. There is more than ten analytical laboratories with and thus the amount of these pesticidal POPs generated increased as
HRGC/HRMS and qualified for the quantitative detection of dioxins. well. Because the generation of solid waste is increasing, large muni-
Data is constantly published on the current levels of PCDD/Fs in soil, cipal solid wastes incinerators are needed to handle the tremendous
sediments and ambient air samples around China. In 1999, State amounts of waste generated every day. In the case of water, about one
Environmental Protection Administration (SEPA) constructed a dioxin third of the industrial waste water and more than 90 percent of
monitoring laboratory in the National Research Centre for household sewage in China is released into rivers and lakes without
Environmental Analysis and Measurement to study the current analysis being treated. In the summer of 2011, the China government reported
and sampling methods for main dioxin sources in order to propose that 43 percent of the state-monitored rivers are so polluted that are
measures for controlling dioxin pollution [125]. An official inventory considered to be unsuitable for human contact [135].
setup by Lin et al. showed that the emission of dioxin from power Studies showed that water bodies located near a highly in-
generation and heat supply, waste incineration, mining, and transpor- dustrialized zone are more prone to POPs contamination. Gulkowska
tation accounted to a total of about 10,237 g TEQ [126]. The con- et al. analyzed Perfluorooctanesulfonic acid (PFOS) and
centration of PCDD/Fs ranged from 275 to 10,780 fg/m3 (18–644 fg I- Perfluorooctanoic acid (PFOA) in seafood samples purchased from fish
TEQ/m3) with an average value of 4355 fg/m3 (268 fg I-TEQ/m3) for markets in Zhoushan and Guangzhou, and China, reporting that PFOS
three districts in Beijing. Li et al. found significant concentrations of were detected in all samples including fish, oysters, crabs, mussels,
PCDD/Fs and PBDD/Fs in the ambient air for four districts of Shanghai clams and mollusks [136]. However, the concentrations weren’t high
[127]. enough to cause immediate health risk to people living in the coastal
Gas/particle partitioning of PCDD/Fs was measured by Xu et al. region of China. Even though no immediate health risk was detected, it
from April 2007 to January 2008 in a satellite town of Eastern China is important to closely and regularly monitor food safety in China.
[128]. The results concluded that the PCDD/Fs levels were higher
during the winter season when compared to the summer season with a 5.5. Dioxin studies in Japan
value in the range of 86–3030 fg/m3. Choi et al. measured PCDD/Fs
level in 142 air samples of Hong Kong [129]. The average PCDD/Fs Studies conducted in Japan reveal that the most important sources
concentration in the air samples obtained from Hong Kong from Jan- for PCDDs/PCDFs are municipal and hazardous waste incineration;
uary 2004 to March 2005 for Tap Mun, Yuen Long, and Tsuen Wan production of iron and steel, copper, lead and zinc; and coal con-
were 1724 fg TEQ/m3, 2927 fg TEQ/m3, and 1875 fg TEQ/m3, re- sumption [137]. In specific, the total dioxin emissions from the use of
spectively. The level of PCDD/Fs in the ambient air of Dalian (2.72 fg agrochemicals in Japan during 1955–1995 were estimated to be about a
TEQ/m3) was found to be lower than the values obtained in Beijing, few hundred thousand kg of PCDD/DFs and 250 kg of WHO-TEQ from
Shanghai, and Hong Kong [125]. From most of the data available, it can pentachlorophenol [138]. The annual deposition flux of dioxins
8
Table 4 were still detected in river water from the deposition of rainfall at
Matrix of Dioxin analysis in Japan [142]. concentrations of 2.4 pg-TEQ/L/year, exceeding the environmental
quality standard (EQS) for water in Japan of 1 pg-TEQ/L [144]. An-
Areas in Japan (Most Matrix Concentration Common Technique of
Populated) Analysis other study, determined the concentrations of PCDDs/Fs and DL-PCBs
in dietary supplement products, containing the oil of fish, marine
Special districts of Tokyo Air 0.2 μg/m3 TO-9 mammals, or egg yolk, on the Japanese market between 2007 and
Water 0.4 μg/m3 USEPA Method 8280
2014. Their results showed that at least in 43 samples of the total of 46
Organisms 2.0 μg/m3 USEPA Method 1613
Sediments 125 μg/m3 USEPA Method 8290 samples, dioxins were detected with concentrations ranging from
0.00015 to 67 pg TEQ/g [145].
Yokohama Air 0.1 μg/m3 TO-9
Organisms 3.0 μg/m3 USEPA Method 1613 5.6. Dioxin studies in the Middle East
Sediments 115 μg/m3 USEPA Method 8290
Osaka Air 3.3 μg/m3 TO-9 One of the major problems with the management of chemicals in
Water 17.2 μg/m3 USEPA Method 8280 many of the Middle Eastern countries, is the lack of information on their
Organisms 11.1 μg/m3 USEPA Method 1613 hazardous characteristics. Other deficiencies include the absence of
unified lists of POPs used, uncoordinated permitting activities, and lack
Nagoya Air 5 μg/m3 TO-9 of information and data on contamination of POPs chemicals in soils,
Water 12.1 μg/m3 USEPA Method 8280 ground water and surface water [146,147]. The sedimentary record of
Organisms 9.1 μg/m3 USEPA Method 1613
PCDD/Fs in the northwestern Arabian Gulf reconstructed from the
analysis of a dated sediment core showed low concentrations at depths.
Sapporo Air 4 μg/m3 TO-9
Concentrations started to increase above the background in the mid-
Organisms 8.0 μg/m3 USEPA Method 1613 1960s attaining a maximum of 7.5 pg/g in the early-1990s and stayed
Sediments 580 μg/m3 USEPA Method 8290 fairly constant thereafter [148]. The concentrations of dioxins found in
Kobe Air 5 μg/m3 TO-9 sediments collected from five locations in Kuwait are among the lowest
Water 15 μg/m3 USEPA Method 8280 reported in the literature for coastal marine sediments with the highest
Organisms 7.0 μg/m3 USEPA Method 1613 concentrations found in sediments collected along a transect facing an
oil loading terminal [149].
Atmospheric concentrations of polybrominated diphenyl ethers
between Feb. 2012 to Feb. 2013 was 3.3 ng-toxic equivalent (TEQ)/m2/ (PBDEs) measured at an urban and a remote location over a twelve-
year with most of the dioxins in the deposition were derived from waste month period in Kuwait. The PBDE concentrations were generally
incinerators [139]. Samples from Chilean city located in the middle of a higher at the urban sites when compared to the concentrations at re-
complex hydrological system with several small urban freshwater mote sites [150]. The most likely source of PBDEs at the remote loca-
bodies along with the River Bio-Bio. The region has numerous industrial tion is thought to be long-range transport from other regions, whereas
and domestic activities that may contribute PCDD/Fs to the environ- at the urban locations other sources such as outgassing of contaminated
ment. The chemical signature of the dioxins and furans found in all air emissions from vehicles and incineration of PBDE containing waste
sediments which suggest that the major contribution to these sediments [150]. The concentrations of PCDD/Fs and dl-PCBs were not controlled
is likely to be from atmospheric deposition caused by vehicle exhaust by temperature variation resulting in the absence of any observed
and biomass burning [140]. Compared to other sites in Yatsushiro, seasonal pattern. A unique dioxin profile was found in the ambient air
Severe contamination and significant sources of PAHs in Tanoura Bay samples collected from the Umm-Al-Aish oil field [151,152]. On the
was observed. However, dioxins and dioxin-like compounds (PCDFs, other hand, PCDDs/Fs concentrations in samples collected from the
and non-and mono-ortho coplanar PCBs) were analyzed in sediments open-burnt municipal landfill site at Marka/Amman have shown high
from eight stations in Tanoura Bay with concentrations were compar- concentrations of PCDD/F ranged from 8.2 to 1470 ng TEQ (BGA)/kg
able to, or lower than at the reference sites indicating that there are no d.w. The total concentrations of PCDD/PCDF were between 685 and
specific sources of these compounds in this Bay [141]. 112,300 ng/kg d.w which is extremely high [153].
Dioxin like materials have been carefully investigated in several El-Kabbanya et al. monitored PCDD/Fs in cement Kiln emissions in
areas in Japan. Table 4 summarizes the sampling locations, matrix of various fuel in Egypt. The data indicates the presence of PCDD/F in
analysis, detected contamination, and the analysis method. As shown in Natural gas, mazout and coke. All of the kiln emission profiles were
Table 4, the amount of dioxins and furans in the water, organisms, found to be same markedly from profiles in ambient air where the small
sediments, and air is determined by the number of industries and the absolute dioxin emission rates from the kilns suggested that kiln im-
nature of their activities in a region. It is also determined by the ap- pacts would be detectable via ambient air monitoring [154]. In addi-
proach used in managing wastes, especially the plastic materials and tion, PFAS concentrations in dust samples collected from three micro
those from healthcare facilities. Special wards of Tokyo and Yokohama environments in Cairo ranged from 1.3 to 69 ng/g with Fluorotelomer
are highly populated areas in Japan; however, they have limited alcohols (FTOHs) being dominant. PFOS was detected in 58% of the
number of industries. The administrations in these municipalities have samples with median concentration of 0.29 ng/g while potassium per-
very strict waste management policies which have directly contributed fluorohexane sulfonate (PFHxS) and perfluorodecane sulfonate (PFDS)
to very low level of dioxins and furans in these two regions. The matrix were below detection limit [155].
shows that these two regions have the least detectable amounts of di- Surface sediments from the Napoleon Gulf and Thurston Bay on the
oxins and furans in air, water, organism, and sediment samples that northern shore of Lake Victoria were analyzed for polychlorinated or-
were tested. On the other hand, Osaka, Nagoya, Sapporo, and Kobe ganic compounds. Fifteen PCDD/Fs and eleven dl-PCBs were found in
have high number of industries. The high industrial activity in these 75.5% of the samples with maximum concentrations of PCDD/Fs and
regions directly correlates with the high amounts of dioxins and furans dl-PCBs were 44.1 and 136 pg g−1 dry weight (dw), respectively
substances in the samples that were tested as presented in Table 4. This [156].
can be attributed to the effluents and emissions from the companies Due to the presence of various resources that might enhance the
[142]. Moreover, dioxin emissions have drastically reduced after the polychlorinated hydrocarbons in the Middle Eastern countries, several
enactment of a law on dioxin emissions [143]. On the other hand, studies evaluated the food intake and the health associated to food
concentrations of dioxin concentrations originated from combustion products with potential contamination. Two commercially important
9
fish species, Nile perch and Nile tilapia belonging to different trophic in the USA the greatest emissions of dioxins were released from
levels were collected from the Napoleon Gulf and Thurston Bay in Lake electricity and heat generating plants, whereas in Canada, burning
Victoria. Moreover, PCDDs, PCDFs and DL-PCBs were extracted from of household garbage has been identified as the largest source of
the fish muscles and livers [157]. The TEQ values were found to be dioxin emissions.
lower compared to those of most fish samples reported in literature and b In the European Union, the highest emissions are reported in
were within permissible levels recommended by the European Union, France, Italy and Spain, mainly due to waste incineration and
implying that the fish was fit for human consumption [157]. On the countries like Turkey, mainly showed effects on the food chain
other hand, it has been reported that the Egyptian total TEQ intake due due to aquatic pollution from industrial discharges.
to the consumption of dairy products, fish/seafood and meat is much c In China, emission of dioxin from power generation and heat
higher than the maximum current WHO-TDI, mainly due to the high supply, waste incineration, mining, and transportation accounted
contamination levels of PCDD/Fs and DL-PCBs reported in the dairy to a total of about 10,237 g TEQ, moreover, rivers have a high
products [158]. Fingerprints of PAHs obtained in the samples suggested level of pollution. In the case of Japan, the high industrial activity
both petrogenic and pyrolytic sources of contamination [159–161]. in these regions, directly correlates with the high amounts of di-
Abdallah et al. determined concentrations of polybrominated diphenyl oxins and furans substances in the samples.
ethers (PBDEs), polychlorinated biphenyls (PCBs) and some organo- d The Middle Eastern data showed that PBDE concentrations were
chlorine pesticides (OCPs) in serum of Egyptian colorectal cancer pa- generally higher at the urban sites when compared to the con-
tients compared to a healthy control group. The results showed no centrations at remote sites. Concentrations from open-burn mu-
significant differences between the levels of target contaminants in nicipal landfill in Jordan showed high total concentrations of
serum of cancer patients and the control group [158]. PCDD/PCDF. Food studies in Kuwait and Egypt, showed that some
Studies on the occurrence of organohalogenated contaminants concentrations were lower than permissible levels, while others,
(OHCs) in human samples from Saudi Arabia have been reported [162]. exceeded accepted concentrations.
Several classes of OHCs were identified in humans from KSA, indicating 4 Finally, in the Middle East, one of the major problems with the
ongoing exposures to already regulated POPs. However, levels of ana- management of chemicals is the lack of readily available informa-
lyzed pollutants were generally on the lower side than studies from tion on their hazardous characteristics. Lack of studies targeting the
different countries [162]. Moreover, Batang, et al. determined the full concentrations and sources of emissions of POPs derivatives in-
PCB profiles in edible fish tissues from the Saudi Red Sea coast [163]. dicating the need for further studies in the region.
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 Acknowledgement
countries [163]. Pesticides residues were extracted from human milk
samples collected from donor mothers in Eastern district of Saudi We thank the Research office at the American University of Sharjah
Arabia [164]. for their Support.
From an initial monitoring study of PCDD/Fs and dl-PCBs in locally
produced and imported food and feed products available across the References
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locally produced and imported food stuffs and animal feed samples dioxins and furans-a review, Int. J. Curr. Res. Rev. 5 (2013) 14–22.
[2] S. Safe, O. Hutzinger, T.A. Hill, Polychlorinated Dibenzo-p-dioxins and -furans
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Trends in Environmental Analytical Chemistry 17 (2018) 1–13

Contents lists available at ScienceDirect

Trends in Environmental Analytical Chemistry

Dioxins and furans: A review from chemical and environmental perspectives T

Fig. 1. Major Dioxins Sources in the Environment.

Method Compounds of Interest Environmental Matrix Analytical Tool References

Fig. 2. Pathways of OH radical addition on HpCDD and OCDD to form a

Various studies have indicated that PCDD/F compounds are sub-

OCDD UV 0.06 [73]

toxic equivalence factor (TEFs) assigned by the World Health

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