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A review on the biogeochemical cycle of Dioxins

ABSTRACT

Dioxins are a group of compounds containing polychlorinated dibenzo-p-dioxins (PCDDs),

polychlorinated dibenzofurans (PCDFs), and co-polychlorinated biphenyls (co-PCBSs). They
are highly stable and toxic. This review comprehensively explains the various sources of
dioxins, their historical background, and their environmental fate. Dioxins enter the
atmosphere and then get attached to the soil particles due to various factors such as P H,
organic matter content. Dioxins enter aquatic systems and subsequently accumulate in
sediments. The uptake of dioxins by aquatic organisms and their bioaccumulation are
discussed. Food consumption is one of the major routes through which dioxins enter human
tissues. It is important to understand the sources, sinks, and the behaviour of dioxins in order
to reduce the levels of dioxins in the environment.

Introduction

Dioxins and Dioxin like compounds (DLCs) such as PCBs, and PBBs are chemical
compounds that are persistent organic pollutants in the environment. Most are by-products of
combustion or various industrial processes.1 PCBs, and PBBs are byproducts of some
unwanted mixtures. Some of the dioxins are very toxic. They are grouped together, as their
mechanisms of action are the same. They activate the AHA (Aryl Hydrocarbon Receptor), but
with different bonding affinities, resulting in different toxicity and other effects. 2
Polychlorinated Dibenzo-P-Dioxins (PCDDs) are derivatives of dibenzo-p-dioxin. TCDD is
the most toxic compound.3 PCDFs (polychlorinated dibenzo-furan) are furans that are
derivatives of dibenzofuran. Polychlorinated biphenyl (PCB) is a derivative of biphenyl.
There are 12 dioxins-like PCBs. In some circumstances, PCBs may partially oxidize to form
dibenzofurans. Dioxins exhibit different levels of toxicity based on the arrangement of
chlorine atoms. The concept of toxic equivalency factor (TEF) has been introduced to
understand the risk assessment. TCDD, is considered the most toxic dioxin and is given a
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TEF value of one. By multiplying the quantity of a specific congener by its TEF gives the
Toxic equivalent amount (TEA).4 Dioxins are hydrophobic in nature and interacts with
organic matter. They are very stable. Therefore, they have the ability to accumulate in the
food chain. The rate of adsorption of dioxins towards soil particles is high.5 Dioxins are
hydrophobic in nature, so the elimination of dioxins from the human body through urine is
difficult. They cannot be metabolized easily and have a higher half-life period. TCDD has a
half-life of 7 years.6 Lipophilicity and stability are proportional to the number of chlorine
atoms. TCDD can be subjected to photodegradation in the presence of UV radiation.7
Microbial degradation is very slow due to the high affinity of dioxins towards soil particles.
In the year 2001 the production and the use of dioxins was banned by The Stockholm
Convention.

Dioxins in the Atmosphere

Figure 1: Sources of Dioxins. (Modified from Kirkok; et. al. SN Applied

Sciences 2020, 2 (10).)19
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The sources and effects of dioxins have been a subject of interest. The research showed an
increase in the levels of dioxins in the environment and ecosystems in the early 1990s and
between 1960 and 1980. The combustion of various materials, chlorinated and consumer
products, pigments, and bleaching paper are primary sources of dioxins. Studies have shown
that the increase in dioxin levels in sediments is proportional to the increase in the
production, use, and disposal of chlorinated organic compounds. Between 1882 and 1962, the
combustion of coal, wood, and peat was the major sources of dioxins. Pentachlorophenol was
the major contributor from 1970 to 1985. Principle component analysis of homologue or
congener-specific data was performed to understand the differences in the profiles of dioxins
and to discuss the differences between media, sites, and contributions from different sources.
Quantitative estimation of source contributions has rarely been performed. In this study,
pentachlorophenol (PCP), CNP (chloronitrophenol) and atmospheric thermal emissions were
the three main sources of dioxins in Lake Shinji. MRA (multiple regression analysis) was
used to calculate their contributions.8 These findings highlight the importance of
understanding the sources and behaviour of dioxins to prevent environmental pollution and
human health risks caused by their persistent nature. Dioxin source identification and

monitoring are essential for developing methods to reduce the levels of dioxins.

Figure 2: Sources of Dioxins in the lake Shinji Basin, Japan. (Modified from Masunaga;
et.al. Environ. Sci. Technol. 2005, 35, 1967-1973.)8
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Dioxins in the Lithosphere

Dioxins are primarily attached to soil particles by adsorption. They are attracted to the surface
of soil particles and adhere to them This process is influenced by the natural chemical
composition of the soil and by the dioxins themselves.8 Factors such as the carbon content of
the soil, the availability of clay minerals, and the specific chemical properties of dioxins play
an important role in the dioxin-soil interactions. These factors affect the ability of dioxins to
bind to soil particles and remain in the environment.9 Dioxins can migrate in the soil through
processes such as leaching and diffusion, although their movement is usually limited by
strong affinity for soil particles but in some cases, dioxins can migrate to the depth of the soil
and can even enter the groundwater.8 Soil properties such as texture, organic matter content,
and PH influence the movement of dioxins in the soil. For example, soils with high organic
matter content shows lower mobility due to the higher sorption, whereas the movement of
dioxins shows higher mobility in soils with lower organic matter.8

Dioxins are present in rural soil at unexpectedly high levels, even in areas isolated from
known anthropogenic sources of dioxin The chemistry of dioxins in soils and deposits
containing smectite clay minerals is not comprehensive. This limits our ability to predict their
fate and control the risks associated with the dioxins. Interactions between neutral organic
compounds (NOCs) and smectite clays are controlled by exchangeable interlayer cations,
structural characteristics of NOCs.9 Dioxins in rocks and their behaviour have been studied
for fields and sediments. Studies have shown that the annual dioxin loss from rice fields is
proportional to the amount of dioxin in the field, and the annual amount of dioxin entering
the lake is proportional to the amount of dioxin lost from the field. The estimated loss of
dioxin from soils in the Lake Shinji basin was found to be about 2% per year, indicating a
half-life of about 35 years This loss mechanism could be runoff, volatilization, decomposition
and burial, highlighting the complex behaviour of dioxins in the lithosphere.9 Historical
trends in dioxin pollution in rocks have been analysed to understand the contributions of
various sources to current trends. The study found that various incinerations, the production
and use of chlorinated organic compounds, and pulp and paper bleaching are major sources of
dioxins. Quantification of source contributions is challenging, but principal component
analysis (PCA) of congener-specific dioxin profiles were used to discuss differences in dioxin
profiles and different sources of contribution.8
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Dioxins in the Hydrosphere

Dioxins can be transported into water through a variety of mechanisms such as surface
runoff, atmospheric deposition, and direct industrial emissions. These mechanisms contribute
to the transfer of dioxins from soil to aquatic systems. The diffusion of dioxins in aquatic
systems is affected by factors such as water flow, temperature, and organic matter. It is also
affected by the hydrophobic nature and the solubility of dioxins. Dioxin sedimentation can
occur through a variety of mechanisms such as settlement of dioxin carrying particles,
transfer from the water column to the sediment, and adsorption to the sediment particles. 10
Over time, dioxins accumulate in sediments due to high their high stability and strong affinity
to the sediment particles. This accumulation allows dioxins to remain in aquatic sediments
longer, posing a threat to aquatic organisms and potentially returning to the water column
through resuspension events.10

The open ocean environment has not shown a decreasing trend in dioxin concentrations and
is acting as a sink for semi-volatile organochlorines used in the tropics. This means dioxins
are transferred from the terrestrial environment into the ocean, where they remain in aquatic
ecosystems.11 Aquatic toxicity studies were conducted on dioxins, which show the effect of
dioxins on the fish and freshwater invertebrates. The bioaccumulation of Dioxins in different
water bird species indicates their potential to bio magnify in aquatic food chains. The
presence of dioxins in water poses a serious threat to aquatic organisms due to their
persistence and potential for adverse effects on species.12

Dioxins in the Biosphere

The levels of organochlorine in marine animals (insects, fish, mammals and seabirds) are
affected by differences in uptake, metabolism and elimination rates. For example,
invertebrates are one of the primary sources of PCBs in the food chain and store polar
metabolites of metabolized PCBs that are then biomagnified in the food chain. Fish and
invertebrate uptake PCBs through food chain transfer and contact with media, while
mammals and birds primarily get PCBs from eating fish. Factors such as metabolism play a
role in bioaccumulation in marine animals. Most congeners are relatively resistance to
metabolism by animals, and resistance to metabolism increases with the level of
chlorination.12 In the Baltic Sea, predatory eagles have been found to have more than 100
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parts per million (ppm) of PCBs (PCBs) and DDT. A blue-white dolphin found in the
Mediterranean coast of France has 833 ppm PCBs.1

Figure 3: Concentration of PCBs, PCDDs, PCDFs in Double crested cormorants and

Hurring gulls from the great lake Michigan. (Modified from Kannan; et.
al. Environmental Science & Technology 2001, 35 (3), 441–447.)20

Biodegradation

Biodegradation of dioxins including polychlorinated biphenyls (PCBs) includes various

mechanisms such as reductive dechlorination, aerobic anaerobic biodegradation,
cometabolism. Microbes such as bacteria and fungi break down dioxins into less toxic
compounds.4 Dioxin biodegradation is driven by favourable environmental conditions such as
optimum temperature, pH, and nutrient availability. Furthermore, the presence of specific
bacterial associations with appropriate electron acceptors (e.g., oxygen, nitrate, sulfate) can
enhance dioxin degradation. In contrast, factors such as extreme PH, nutrient deficiency,
presence of inhibitors can prevent microbial dioxin degradation.11 Dioxins enter the food
chain primarily through environmental pollution. Sources of dioxin pollution include
industrial disposal, waste incineration, and agricultural practices. Once released into the
environment, dioxins can attach to soil particles, accumulate in plants, and then pass from
herbivores to predators through food or water contamination.10 In aquatic ecosystems, dioxins
accumulate in organisms such as fish, worms, and aquatic plants. This bioaccumulation
results from the absorption of dioxins by aquatic organisms through direct contact with
contaminated water and sediments, and from the uptake of contaminated prey.12

Human exposure
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Dioxins go through different trophic levels in the food chain. The chain contains primary
producers such as plants and algae, which absorb dioxins from the environment. These
dioxins enter into the herbivores that consume those plants and algae. Dioxins get
accumulated in their tissues. When carnivores eat these herbivores, dioxins enter into their
bodies causing more bioaccumulation in their bodies. The main routes of human exposure are
consumption of contaminated animal products such as meat, dairy and fish, and contaminated
fruits and vegetables Furthermore, occupational exposure in the industries of waste
incineration and chemical processing leads to the exposure to dioxins.8 The implications for
human health risks are noteworthy, as dioxin exposure is associated with adverse health
effects, including systemic, immune, neurological, reproductive, developmental , and
genotoxic effects, and increased risk of cancer.13

Formation of Dioxin from chloro and bromo phenols

Dioxins are produced by the high temperature oxidation of chloro, bromo phenols. There are
several key mechanisms in this oxidation reaction. Dibenzo-p-dioxin (DD) and 4,6-
dibromodibenzofuran (4,6-DBDF) are produced by homogenous, gas-phase oxidative thermal
decomposition of 2-chlorophenol and 2-bromophenol. Hydroxyl-hydrogen loss, simple
substitution reactions, formation of stable phenoxyl radicals, and chlorination of chlorophenol
are the key steps involved in the formation of dioxins. Addition of oxygen (O2) accelerates
the decomposition of chlorophenols at low temperatures compared to thermal conditions.14

Long range transportability

The identification of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/PCDFs)

has been a topic of interest. Rain water and soil samples were used to investigate the
contribution of airborne PCDD/PCDF concentrations. Factor analysis was used to find the
similarities, differences, and relationships among changes in the depositional fluxes.15

The levels and profiles of Polychlorinated Naphthalene (PCN) in Toronto’s urban air are
affected by current combustion sources. High-volume air samples taken from two sites in
Toronto (UT and MSC) revealed different concentrations of PCN. UT’s downtown site had
higher levels of PCN, which were attributed to evaporation from past uses and the disposal of
PCN/PCM mixtures. MSC’s more industrial site showed PCN profiles that indicated inputs
from combustion- sources.16
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It is clear from numerous studies that Dioxins are dispersed and transported through different
environmental routes. The main sources of Dioxins are PCP, CNP, and combustion.8 Dioxins
present in the atmosphere are associated with long-distance transport from biomass burnings
in Southeast Asia affecting air quality in places like Taiwan.17 In addition, dioxin and other
pollutants found in Great Lakes area bird eggs suggest a wide range of chemicals are present
in the environment. Dioxins in Lake Shinji Basin, Japan Congener-specific dioxin analysis
was used in a study of the lake’s surface sediment to identify three primary dioxin sources
(PCP, CNP, and combustion), with significant contribution from recent surface sediment. 8
The examination of soil samples from Korea has shown that the majority of polychlorinated
dibenzo-p-dioxin-dibenzofurans (PCDDs/DFs) present are tetra- to octa chlorinated, with
total concentrations ranging from 35 to 121,400 pg/g, dry weight. The study also identified
potential sources of contamination, such as industrial areas and open incineration of industrial
wastes.18

Conclusion:

This review comprehensively explains the biogeochemical cycle of dioxins. Dioxins are
highly toxic in nature. They are chemically and thermally stable in the environment. So,
therefore it is necessary to understand the sources and sinks of dioxins in order to develop
effective methods to control them. There are various sources of dioxins such as industrial
waste, incineration, and combustion. Dioxins are released into the atmosphere and then get
deposited in the soils due to their highly adsorption tendency to organic matter. They enter
into water through various mechanism such as leaching of soils, industrial emissions.
Ingestion of dioxins by fish causes bioaccumulation. Consumption of fish by carnivores leads
to biomagnification of dioxins. Food is one of the primary sources which contains dioxins.
Biodegradation of dioxins by enzymes can take place under favourable conditions. Congener-
specific dioxin analysis in Lake Shinji identified PCP, CNP and combustion as the three
primary sources of dioxins. Biomass burning produces a significant number of dioxins, which
affects air quality. This review highlights the environmental fate and behaviour of dioxins in
the atmosphere, lithosphere, biosphere, and hydrosphere. There is a significant need for more
research and continued monitoring of dioxins to reduce their levels in the atmosphere.
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