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MARINE ENVIRONMENTS: DIVERSITY, THREATS AND

CONSERVATION (ISBN: 978-1-53618-874-5)


LINA CHARLES (EDITOR)
2021
Nova Science Publishers

Chapter 3

ORGANOCHLORINE PESTICIDES (OCPS) IN


COASTAL MARINE ENVIRONMENTS:
LEVELS, FATE, BEHAVIOR, AND EFFECTS
ON BIOTA

Lautaro Girones1, Pilar Palacios1, Ana Laura Oliva1,


Jorge Eduardo Marcovecchio1,2,3,4
and Andrés Hugo Arias1,5,*
1
Instituto Argentino de Oceanografía (CONICET/UNS), Bahía Blanca,
Provincia de Buenos Aires, Argentina
2
Universidad de la Fraternidad de Agrupaciones Santo Tomás de
Aquino, Mar del Plata, Provincia de Buenos Aires, Argentina
3
Universidad Tecnológica Nacional – FRBB, Bahía Blanca,
Provincia de Buenos Aires, Argentina
4
Academia Nacional de Ciencias Exactas, Físicas y Naturales,
Ciudad Autónoma de Buenos Aires, Argentina
5
Departamento de Química, Universidad Nacional del Sur,
Bahía Blanca, Provincia de Buenos Aires, Argentina

*
Corresponding Author’s Email: aharias@iado-conicet.gob.ar.
2 Lautaro Girones, Pilar Palacios, Ana Laura Oliva et al.

ABSTRACT
Pesticides have been extensibility used in the control of agricultural and
sanitary pests. From World War II onward, more efficient and cheaper
synthetic pesticides, such as organochlorine pesticides (OCPs), including
DDT, lindane, or endosulfan, replaced the relatively environmentally
friendly pesticides. OCPs were widely used worldwide; however, in the
1970s these compounds were began banned due to their harmful effects on
both, biota and humans. Nevertheless, half a century later, due to their high
persistence and the existence of some active sources, OCPs remain a
problem for the health of marine ecosystems.
Once in the environment, their distribution depends on the interaction of
several factors -explained in detail in this chapter- such as the physical-
chemical properties of each compound; interactions with the matrix;
characteristics of the environment; and intensity, distance, and seasonality
of the source, between others.
This chapter reviews current levels, environmental behavior and fate, and
effects on biota of organochlorine pesticides in global marine coastal
environments, noting that these compounds are still detectable and could
be harmful to marine biota.

Keywords: persistent organic pollutants, organochlorine pesticides, DDT,


lindane, endosulfan, coastal environments, marine pollution,
environmental fate, environmental behavior

INTRODUCTION

Pesticides have been used to control pests in agriculture for over 4,500
years. Until the mid-1900s, inorganic compounds, such as sulfur and copper,
and plant extracts were used. In the first decades of the XX century, new
synthetic pesticides such as organochlorine pesticides (OCPs) were
developed; for instance, during the Second World War, these substances
were used to control insect vectors of disease. At the end of the war, OCPs
were adapted for pest control in agriculture and public health, being
considered a miraculous pesticide due to their high effectiveness and low
cost. However, in 1962, Rachel Carson documented the environmental
impacts, especially on bird populations, of the widespread use of DDT in the
Organochlorine Pesticides (OCPs) in Coastal Marine Environments 3

United States, in the famous book “Silent Spring”. This publication


highlighted the collateral effects of the inappropriate use of some chemical
substances and the controversy between benefits and costs that accompany
the industrial growth and the welfare state. The publication raised the alarm
of public and political opinion, generating environmental movements and
massive protests, which ended with the banning, from 1972, of the
agricultural use of DDT and other organochlorine pesticides in many
countries (Hayes and Hansen 2017).
After the 1960s and 1970s, the harmful effects of pollutants and their
presence in the environment began to be studied, and our knowledge of
chemicals is quite extensive. However, new substances that threaten the
environment are created daily, and sometimes, the discovery of their harmful
effects arise too late. This was the case with the OCPs, which despite having
been banned or restricted in almost all countries, they are still being
detecting in the environment. Moreover, due to their long-term toxicity,
sometimes, current environmental levels could pose a risk to biota (Girones
et al. 2020) since even when environmental concentrations are low they can
cause damage to the biota (Petrovic et al. 2013; Sosa-Ferrera et al. 2013).
Marine pollution processes are one of the most important problems
which humanity is facing at present (Lohmann 2007). Among the most
affected marine environments, coastal environments stand out as the
heaviest chemically polluted. These are the areas where the main aquatic and
terrestrial interactions occur. On the one hand, waste or effluents that come
from different sources (urban, industrial, or agricultural) are dumped directly
(sewage, landfills) or through rivers due to runoff. On the other hand, many
coastal environments, especially semi-closed ones such as bays, estuaries,
fjords, or coastal lagoons, have great potential to accumulate organic
pollutants because the loss of pollutants by export and dilution is limited by
the long residence times of water (Diamond et al. 2005), and also because
the adsorbent materials levels, especially organic carbon, are generally high.
Further, coastal areas, including coastal wetlands such as coral reefs,
mangroves forest, salt marshes, or seagrass beds, are very important to biota
and humans because they provide invaluable ecosystem services, such as
4 Lautaro Girones, Pilar Palacios, Ana Laura Oliva et al.

refuge, cross-ecosystem nutrient transfer, erosion control, and pollution


control, between others (Barbier et al. 2011).
Then, considering this complex scenario, this chapter aimed to
comprehensively review the available organochlorine pesticides data about
their distribution, production, regulation, main current sources, physic-
chemical properties, environmental fate and behavior, documented effects
on marine biota and humans, and the current levels in global coastal and
marine sediments.

PRODUCTION AND USE

The first organochlorine pesticide massively used worldwide was DDT,


beginning in 1939 when Paul Hermann Muller discovered its properties as
an insect poison and its low toxicity to humans. DDT was indiscriminately
used during World War II (1939-1945), to protect soldiers and civilians
against insect-borne diseases such as malaria, dengue, and typhus (Wheeler
1946). After the war, the used amounts increased exponentially (Hayes
1991). The effectiveness, persistence, versatility, and low cost turned DDT
massive in agriculture, forestry, and public health for 30 years (USEPA
1975). In addition to protecting crops and kill household insects, the use of
DDT for public health avoided the death of more than 5 million people per
year worldwide. Thus, for example, in India, there were 75 million malaria
cases in 1952 and after using DDT massively, only 100,000 cases have been
registered in 1964 (WHO 1971). Regarding the agricultural purposes of
DDT, it was used in a wide variety of crops, reaching more than 36,000 tons
per year until its prohibition or restriction (Hayes and Hansen 2017).
Currently, the World Health Organization recommends the use of DDT in
areas where malaria is a public health problem due to its effectiveness in its
control (WHO 2006), and so that, about 3,300 tons are produced annually
worldwide (Hayes and Hansen 2017). Given the proven insecticidal
capabilities of DDT, after World War II, other organochlorine pesticides
with similar features were synthesized, such as chlordane (1945); aldrin and
dieldrin (1948); heptachlor (1949); toxaphene (1949); endrin (1951);
Organochlorine Pesticides (OCPs) in Coastal Marine Environments 5

endosulfan (1956); hexachlorocyclohexane (HCH and lindane; 1940), and


mirex (1950; Kennish 1997). These pesticides showed several uses and
applications depending on their characteristics and regions (UNEP 2003).
Following DDT, the most popular OCP worldwide was
hexachlorocyclohexane (HCH) as lindane (pure γ-HCH) or technical HCH
(a mixture of various isomers, including α-HCH, 55-80%, β-HCH, 5- 14%,
and γ-HCH, 8-15%), which was used as a broad-spectrum insecticide in
seeds, soils, foliage, trees, fabrics, and wood, as well as a treatment against
ectoparasites in veterinary and human applications. Voldner and Li (1995)
estimated the global use of 550,000 tons of technical HCH and 720,000 tons
of lindane between 1948 and 1993. Another group widely used worldwide
was the cyclodienes, which includes aldrin, dieldrin, endrin, chlordane,
heptachlor, and endosulfan. Aldrin and dieldrin were used as insecticides
(1950-1970) to control soil insects, the corn rootworm, the rice weevil, the
grasshopper, and for crops of corn, potatoes, and cotton, and for protect
wooden structures from termites. Endrin was used as an insecticide in cotton,
rice, sugar cane, corn, and other cereal crops, and as a rodenticide in orchards
(Larini 1999; UNEP 2002). Meanwhile, chlordane was mainly used as an
insecticide in rice, oilseeds, corn, sugar cane, and citrus crops, and in the
control of domestic pests (e.g., cockroaches, ants, and termites). Heptachlor
was used primarily in the control of soil insects and termites, and,
sometimes, it was used against cotton insects, grasshoppers, and some crop
pests, such as sugarcane, as well as to fight malaria. Endosulfan is a broad-
spectrum acaricide and insecticide, for agricultural or domestic use, in a
wide variety of vegetables, fruits, cereals, and cotton, as well as ornamental
shrubs, trees, vines, and ornamental plants (Ulberth 2000), wood
preservation (UNEP 2002), and in the control of vectors of diseases such as
the tsetse fly (Li and Macdonald 2005). Another important group of OCPs
was the cyclopentadienes, including toxaphene and mirex. The first was
used intensively (450,000 tons from 1950 to 1993 according to Voldner and
Li, 1995) as an insecticide and acaricide in cotton, cereals, fruits, nuts, and
vegetable crops, and in the control of ectoparasites in livestock, such as lice,
flies, ticks, scabies, and mites. While the second, mirex, was used mainly for
the ant’s control and, lesser degree, as a flame retardant in plastics, paint,
6 Lautaro Girones, Pilar Palacios, Ana Laura Oliva et al.

paper, and electrical equipment (UNEP 2002). Meanwhile, the


hexachlorobenzene (HCB) has been a fungicide used since 1945 to treat
grain crops and to manufacture inks, fireworks, ammunition, and synthetic
rubber. This compound is also a by-product of the manufacture of
chlorinated industrial chemicals, such as solvents (e.g., carbon tetrachloride,
trichloroethane, and pentachlorobenzene) and various pesticides (e.g.,
pentachlorophenol, dicloram), and the incineration of chlorinated waste.

MANAGEMENT

In 1962, Rachel Carson published “Silent Spring”, the first ecological


manifesto against the indiscriminate use of organochlorine compounds.
There she denounced that the widespread use of DDT could be the main
cause of the population reduction of various bird species, many of them
occupying the top of the food chain, such as the peregrine falcon and the
bald eagle, symbol of the United States (Baird 2018; D’Amato et al. 2002).
Because of the results of this and other studies presented by the scientific
community, Sweden, in January 1970, was the first country to ban chlorine
insecticides (D’Amato et al. 2002). In the same year, the ex-USSR banned
the use of DDT as a household pesticide and, in 1981, as an agricultural
pesticide, except for use in disease control programs (Turusov et al. 2002).
Between 1970 and 1980, the use of pesticides was banned in most developed
countries (Kutz et al. 1991). It took a few more years for developing
countries to ban or restrict their use, either by their own regulations or by
signing international conventions. In 1998, the UN countries signed the
Rotterdam Convention, where guidelines for the transport, storage, and
disposition of organochlorines were proposed (Hough, 2000). Years later, in
2001, they signed the Stockholm Convention, which entered into force in
May 2004, where the progressive elimination or minimization of the use and
production and the safe elimination of an initial list of twelve contaminants
was proposed. These compounds and those added later are considered
persistent organic pollutants (POPs) due to their high environmental
persistence, toxicity, and ability to bioaccumulate and transport long
Organochlorine Pesticides (OCPs) in Coastal Marine Environments 7

distances. Among the POPs listed in the Stockholm Convention are the
following organochlorine pesticides: aldrin, endrin, dieldrin, chlordane,
heptachlor, DDT, HCB, mirex, and toxaphene, added to the initial list that
entered into force in 2004; α-HCH, β-HCH, γ-HCH (lindane), and
Chlordecone, added in 2009; and endosulfan and Dicofol, incorporated in
2011 and 2019, respectively. However, the Stockholm Convention notes
exceptions to the use of some pesticides: DDT can be used in the fight
against disease vectors when there are no safe, effective, and affordable local
alternatives; endosulfan can be used in specific crop and pest combinations;
lindane can be used as a second-line treatment for the control of pediculosis
and scabies in humans.

CURRENT SOURCES TO COASTAL ENVIRONMENTS

Although the use and production of organochlorine pesticides have been


restricted worldwide since the 1970s, the marine environment continues
incorporating them. One of the main sources is the continental exports from
obsolete reserves and contaminated areas, which act as secondary sources.
In a global report published in 2003 (UNEP 2003) and many current national
implementation plans, it was observed that information on OCPs stockpiles
in most developing countries is poor, scarce, or null (UNEP 2003, Girones
et al. 2020). Anyway, the UNEP global report (UNEP 2003) was able to
record the existence of large stockpiles in Europe (80,000 tons, mainly in
central and eastern Europe) and in Sub-Saharan Africa (120,000 tons).
Moreover, agricultural and urban soils where pesticides were used or
produced in the past and river sediments associated with these areas
constitute deposits that slowly release pesticides into the marine
environment, reaching the coastal waters by processes, which will be
explained later.
Another current source for the marine environment, probably less
important due to its severe restriction, is the use and legal production of some
OCPs. These are contemplated in the exceptions of international treaties and
some national laws.
8 Lautaro Girones, Pilar Palacios, Ana Laura Oliva et al.

Finally, a potentially important source appears to be the illegal use of


pesticides in agriculture in some countries (Van Den Berg et al. 2017).
Several authors observed patterns between the parent pesticides and their
metabolites (e.g., DDT/(DDE + DDD) and technical endosulfan/ endosulfan
sulfate) that would indicate recent use of them ( Carvalho et al. 2009; Chen
et al. 2020; Girones et al. 2020; Jin et al. 2017; Rizzi et al. 2017a).

ENVIRONMENTAL FATE AND BEHAVIOR OF OCPS

Once OCPs enter the environment, their fate, behavior, and spatio-
temporal distribution are controlled by a combination of three groups of
factors (Mackay et al. 2006). First are the physic-chemical properties of
pollutants such as molecular composition, structure, weight, and volume,
and solubility in the different media, which influence the partition and
reaction trends between environmental compartments and the rate of
degradation in other chemical species. Second are the environmental
conditions such as temperature, fluxes, and the composition of the various
environmental compartments, i.e., air, water, and solids. Third are the
patterns of use/release to the environment, such as the periodicity and
intensity of the source.

Factor: Nature and Physic-Chemical Properties of OCPs

Organochlorine pesticides are a group of chemicals that share certain


structural characteristics. They have a highly chlorinated aliphatic or
aromatic cyclic structure, and in some cases are associated with oxygen or
sulfur atoms. Consequently, most OCPs are resistant to biological, physical,
and chemical degradation. This makes the behavior profiles of the OCPs in
the environment, such as the phase distribution and the transport processes,
tend to play a fundamental role in the control of their environmental fate and
distribution. The variability in these profiles, usually, is attributed to some
key physicochemical properties inherent in each chemical compound:
Organochlorine Pesticides (OCPs) in Coastal Marine Environments 9

solubility in water, solubility in octanol, vapor pressure, the three partition


coefficients between air, water, and octanol (Figure 1), and susceptibility to
degradation or transformation reactions. Furthermore, other essential
molecular descriptors are molar mass and molar volume.
Solubility is the maximum ability of a solvent, such as distilled water or
octanol, to dissolve chemicals. Since most OCPs exhibit low solubility in
water, which is even lower in seawater due to the salty effect, up to 5.8 times
lower (Cetin et al. 2006), and high solubility in octanol (a compound
assimilable to lipids and organic matter) the octanol-water partition
coefficient (KOW) is high, i.e., they are hydrophobic and lipophilic.
Meanwhile, the vapor pressure (VP), which can be considered as “air
solubility”, is the saturation concentration or solute pressure in a gas phase,
and is expressed as mol/m3. The relationship between VP and the solubility
in water (mol/m3) determines Henry’s law constant (H; Pa.m3/mol) and the
partition coefficient between air and water (KAW), which is calculated as
KAW = H/RT, where R is the ideal gas constant (8,314 J/mol.K) and T is the
absolute temperature (K). Vapor pressure affects the atmospheric transport
of the OCPs. Compounds with the higher VP reach longer distances to the
source (Muir et al., 1999), therefore, the different congeners of the same
pesticide but with different VP, such as the - -, and -HCH isomers, leave
the atmosphere at different speeds due to precipitation and air-water gas
deposition, resulting in discrimination in long-distance transport (Iwata et
al. 1993). However, there is a common misconception that substances with
very low VP, i.e., “non-volatile” (or very poorly soluble in the air) such as
DDT and other OCPs, cannot partition to the atmosphere (Mackay et al.
2006). This is not necessarily the case because these substances also have
low solubility in water, therefore Henry’s law constants are relatively high
and can be appreciably divided from water to the atmosphere (Mackay et al.
2006). This partition is very sensitive to change in temperature due to the
large enthalpy change associated with transfer to the vapor phase, which
would explain the global distillation of OCPs, evaporating in warm areas
and condensing in cold areas.
Another important partition coefficient to understand the environmental
behavior of OCPs is the octanol-air partition coefficient, KOA, which is
10 Lautaro Girones, Pilar Palacios, Ana Laura Oliva et al.

mainly used in continental environments to evaluate the diffusive exchange


between air and foliage, aerosol particles, or soils (Finizio et al. 1997;
Mackay et al. 2006), and is calculated experimentally, although it generally
follows this equation: KOA = KOW/KAW.
In addition to KOW, KAW, and KOA (Figure 1), other partition coefficients
are used to model and predict the environmental fate of OCPs, such as KOC
(organic carbon-water partition coefficient), KD (sorption partition
coefficient for all the soil on a dry weight basis), KOM (organic matter-water
partition coefficient), and KB or BCD (water-to-fish bioconcentration
factor). These coefficients are calculated from laboratory or field
measurements or are estimated from the relationship with other coefficients,
for example, KOC is often estimated to be equivalent to 0.35 KOW (Seth et al.
1999), KOM is 0.56 KOC (i.e., 56% organic carbon in organic matter; Mackay
et al. 2006), and KB is 0.05 KOW (i.e. 5% lipid in fish; Mackay 1982).
However, these estimates can vary considerably from the real values due to
the complexity of the matrices and environmental conditions, either due to
the variation in pH, content and type of organic carbon, temperature,
pollutant concentration, polarity, and age, or the metabolic capacity of the
organisms, and so that, care must be taken when using them.
MARINE ENVIRONMENTS: DIVERSITY, THREATS AND CONSERVATION (ISBN: 978-1-53618-874-5)
LINA CHARLES (EDITOR)
2021
Nova Science Publishers

Figure 1. Diagram of relationships between the three solubilities (CA, CW, CO) and the three partition coefficients (KAW, KOW, KOA).
Table 1. General characteristics and physicochemical properties of parents organochlorine pesticides and their
main metabolites: Common name - IUPAC name; CAS number [x-x-x]; molecular formula and structure;
molecular weight (MW); melting point (MP); water solubility (Sw, mg/L at 25°C); vapor pressure (VP, Pa at
25°C); Henry’s Law constant (H, Pa.m3.mol-1); octanol-water partition coefficient at 25°C (log KOW); octanol-
air partition coefficient at 25°C (log KOA); organic carbon-water partition coefficient at 25°C (log KOC); Half-
life class in air (A), water (W), and sediment (S): 1 (<10 h), 2 (10-30 h), 3 (30-100 h), 4 (100-300 h),
5 (300-1000 h), 6 (1000-3000 h), 7 (3000-10000 h), 8 (10000-30000 h), 9 (> 30000 h)

p,p’-DDT - 1,1,1-trichloro-2,2-bis-(4-chlorophenyl)-ethane
[50-29-3] C14H9Cl5 MW: 354.49 MP: 108.5 Sw: 0.149 VP: 0.0005
H: 1.100 log KOW: 6.39 log KOA: 9.73 log KOC: 5.4 Half-Life. A:4 ; W:7 ; S:9

p,p’-DDE - 1,1-dichloro-2,2-bis-(p-chlorophenyl)-ethylene
[72-55-9] C14H8Cl4 MW: 318.03 MP: 89 Sw: 0.251 VP: 0.003
H: 4.200 log KOW: 6.93 log KOA: 9.70 log KOC: 5.0 Half-Life. A:4 ; W:9 ; S:9

p,p’-DDD - 1,1-Dichloro-2,2-bis (4-chlorophenyl)ethane


[72-54-8] C14H10Cl4 MW: 320.04 MP: 109.5 Sw: 0.736 VP: 0.001
H: 0.500 log KOW: 6.33 log KOA: 10.03 log KOC: 5.0

Methoxychlor - 1,1,1-trichloro-2,2-bis(4-methoxy-phenyl)ethane
[72-43-5] C16H15Cl3O2 MW: 345.65 MP: 87 Sw: 0.045 VP: 0.001
H: 0.999 log KOC: 4.9 Half-Life. A:2 ; W:4 ; S:7

Hexachlorocyclohexane (HCH) - 1,2,3,4,5,6-Hexachlorocyclohexane


α-HCH [319–84–6] C6H6Cl6 MW: 290.83 MP: 158 Sw: 1.000 VP: 0.100
H: 0.872 log KOW: 3.81 log KOA: 7.46 log KOC: 3.8
β-HCH [319–85–7] C6H6Cl6 MW: 290.83 MP: 309 Sw: 0.100 VP: 0.026
H: 0.116 log KOW: 3.80 log KOA: 8.74 log KOC: 3.4
γ-HCH [58-89-9] C6H6Cl6 MW: 290.83 MP: 112.5 Sw: 7.300 VP: 0.027
H: 0.149 log KOW: 3.70 log KOA: 7.74 log KOC: 3.0 Half-Life. A:5 ; W:8 ; S:9
δ-HCH [319–86–8] C6H6Cl6 MW: 290.83 MP: 141.5 Sw: 8.000 VP: 0.027
H: 0.073 log KOW: 4.14
Aldrin - 1,2,3,4,10,10-hexachloro-1,4,4a,5,8,8a-hexahydro-1,4-endoexo-5,8-dimethano-naphthalene
[309-00-2] C12H8Cl6 MW: 364.9 MP: 104 Sw: 0.985 VP: 0.064
H: 23.000 log KOW: 6.24 log KOA: 8.26 log KOC: 2.6 Half-Life. A:4 ; W:8 ; S:9

Dieldrin - 1,2,3,4,10,10-hexachloro-6,7-epoxy-1,4,4a,5,6,7,8,8a-octahydro-exo-1,4-endo-5,8-dimethanonaphthalene
[60-57-1] C12H8Cl6O MW: 380.91 MP: 175.5 Sw: 4.952 VP: 0.014
H: 1.100 log KOW: 5.48 log KOA: 8.84 log KOC: 4.1

Endrin - 1,2,3,4,10,10-hexachloro-6,7-epoxy-1,4,4a,5,6,7,8,8a-octahydro-=exo-1,4-exo-5,8-dimethanonaphthalene
[72-20-8] C12H8Cl6O MW: 380.91 MP: 245* Sw: 1.143 VP: 0.003
H: 1.100 log KOW: 4.94 log KOA: 8.32 log KOC: 4.0

Chlordane - 1,2,4,5,7,8,8-octachloro-3a,4,7,7a-tetrahydro-4,7-methanoindane
Cis- [57-74-9] C10H6Cl8 MW: 409.78 MP: 106 Sw: 0.533 VP: 0.007
chlordane H: 5.700 log KOW: 6.20 log KOA: 8.83 log KOC: 5.5 Half-Life. A:4 ; W:8 ; S:9
Trans- [5103-74-2] C10H6Cl8 MW: 409.78 Sw: 0.615 VP: 0.010
chlordane H: 6.800 log KOW: 6.27 log KOA: 8.83 log KOC: 5.5 Half-Life. A:4 ; W:8 ; S:9
Endosulfan [115-29-7] - 6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a–hexahydro-6,9-methano-2,4,3-=benzodioxathiepin-3-oxide
α isomer [959–98–8] C9H6Cl6O3S MW: 406.93 MP: 106 Sw: 2.564 VP: 0.004
H: 0.700 log KOW: 4.94 log KOA: 8.49 log KOC: 3.4
β isomer [33213–65–9] C9H6Cl6O3S MW: 406.93 MP: 207-209 Sw: 36.216 VP: 0.004
H: 0.045 log KOW: 4.78 log KOA: 9.53 log KOC: 3.5
Endosulfan sulfate - 6,7,8,9,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepin-3,3-dioxide
[1031–07–8] C9H6Cl6O4S MW: 422.93 MP: 181

Heptachlor - 1,4,5,6,7,8,8-heptachloro-3a-4,7-7a-tetrahydro-4,7-endo-methanoindene
[76-44-8] C10H5Cl7 MW: 373.32 MP: 95.5 Sw: 1.307 VP: 0.130
H: 38.000 log KOW: 5.94 log KOA: 7.76 log KOC: 4.4 Half-Life. A:3 ; W:5 ; S:7
Heptachlor epoxide - 1,4,5,6,7,8-heptachloro-2,3-epoxy-2,3,3a-4,7,7atetrahydro-4,7-methanoindene
[1024–57–3] C10H5Cl7O MW: 389.32 MP: 160 Sw: 5.061 VP: 0.022
H: 1.700 log KOW: 5.42 log KOA: 8.59 log KOC: 4.0

Table 1. (Continued)

Mirex - 1,1a,2,2,3a,4,5,5,5a,5b,6-dodeca-chlorooctahydro-1,3,4-metheno-1H-cyclobuta(cd)pentalene
[2385-85-5] C10Cl12 MW: 545.54 MP: 485 Sw: 0.000065 VP: 0.0001
H: 839.400 log KOW: 6.90 log KOC: 6.0 Half-Life. A:4 ; W:6 ; S:9

Toxaphene - 1,4,5,6,7,7-hexachloro-2,2-bis(chloromethyl)-3-methylidenebicyclo[2.2.1]heptane (Mixture of chlorinated camphene with


67–69% Cl content)
[8001-35-2] C10H10Cl8 MW: 413.81 MP: 65-90 Sw: 0.500 VP: 0.0009
H: 0.745 log KOW: 5.50 log KOC: 5.0

Hexachlorobenzene (HCB) – hexachlorobenzene


[118–74-1] C6Cl6 MW: 284.78 MP: 228.83 Sw: 0.399 VP: 0.094
H: 65.000 log KOW: 5.64 log KOA: 7.21 log KOC: 4.9 Half-Life. A:8 ; W: 9 ; S: 9

*Water solubility (mg/L at 25ªC), Vapor pressure (Pa at 25ªC), Henry’s Law Constant (H/Pa.m3.mol-1), log KOW, and log KOA, for hexachlorocyclohexanes, methoxychlor, mirex, HCB, and toxaphene
were selected from Mackay et al. (2006), and for the other compounds from Shen and Wania (2005). Log K OC and half-life in the air (A), water (W), and sediment (S) for all compounds were
selected from Mackay et al. (2006).
Organochlorine Pesticides (OCPs) in Coastal Marine Environments 15

Another characteristic that notably affects the environmental fate and


distribution of OCPs is their half-life in the environment. Since this is
affected by the nature of the compartments and the environmental
conditions, it is impossible to document a single reliable value for this
parameter. However, a quite reliable half-life range can be established for
each compound. Hence, Table 1 summarizes the ranges for the half-life of
the OCPs estimated for average environmental conditions according to
Mackay et al. (2006) for the main abiotic media: air (A), sediment (S), and
water (W). Given the different exposures to weathering agents, in general,
the OCPs half-life class in water is 3 times higher than in air (30 times slower
degradation) and the half-life class in sediments is 2 times higher than in
water; i.e., if the half-life class in the air is 2, in water will be 5 and in
sediments will be 7. This is summarized and shown in Table 1, in
conjunction with the structure and physicochemical properties of parent
OCPs and their main metabolites.

Factor: Environmental Characteristics and Conditions

As mentioned above, knowing the physicochemical properties of OCPs


is not enough to understand and predict their behavior and environmental
fate, it is also necessary to know the advective transport, the phase
heterogeneity, and the prevailing environmental conditions (Ciffroy 2018).
Advective transport is understood as the transport of the pollutant given by
the movement of the phases in which it is dissolved or associated, for
example, the movement of air masses and water in a river or ocean currents,
and sedimentation or sediment resuspension (Figure 2). While the
heterogeneity of the phases is understood as the presence of different
fractions or domains within the same environmental compartment
(atmosphere, water, soil, or sediment; Figure 2). The partition between the
different fractions or domains of each compartment is a determining factor
in the distribution, bioavailability, and toxicity of OCPs and, therefore, their
study is essential to understand the environmental behavior of OCPs.
16 Lautaro Girones, Pilar Palacios, Ana Laura Oliva et al.

Figure 2. Schematic representation of the main organochlorine pesticide fate processes


in coastal environments. A: air; AP: air particulate fraction; AD: air dissolved fraction;
W: water; WP: water particulate fraction; WD: water dissolved fraction S: sediment; SP:
sediment particulate fraction; SD: sediment dissolved fraction; C: consumer (C1, C2,
C3: trophic levels); Ph: producers; SOAGR: agricultural soil; SONAT: natural soil; SOU:
Urban soil; SWU and SWI: urban and industrial sewage; Veg: vegetation.

Water
Despite being hydrophobic, water is the main transport means for OCPs
from their source to their sink, i.e., the atmosphere, sediment, or biota. Rains
can wash particles or water from OCP-contaminated stockpiles or soils into
rivers or storm/sewage drains by runoff and subsequently discharge them
into the sea (Figure 2). At all stages (source, transport, and sink) several
processes affect the phase distribution of the OCPs, mainly, the division
between fractions of the same phase and other phases, and loss due to
degradation or irreversible sorption.
As can be seen in Table 1, the KOW range is from x to x showing low
water solubilities, hence, the OCPs tend to concentrate in the water
Organochlorine Pesticides (OCPs) in Coastal Marine Environments 17

particulate fraction. This trend is even greater in salty media because the
solubility of OCPs can be up to 5.8 times lower than in distilled water due
to the salty effect (Cetin et al. 2006).
The fraction of particles comprises solids that, according to their mass
and the predominant local hydrodynamics, remain as suspended particles or
yield to gravity, settling and becoming the sediment bed. Due to its high
affinity for particles, the OCPs distribution both in sediments and in water
in marine coasts is generally associated with the sedimentation patterns
characteristic of inland discharges, in which coarser particles precipitate
near the river mouth and finer and lighter particles and colloids (particles of
ø <1 µm) precipitate further away or remain in suspension (Burgess 2012).
However, other processes such as resuspension, bioturbation, turbulence,
and changes in salinity and temperature play an important role in the fate of
particles and OCPs in these environments (Ciffroy 2018).

Sediment
Dissolved, organism-accumulated, or particle-associated OCPs in the
water column can become part of the sediment by advective transport, e.g.,
precipitation of particles or organic matter, and, lesser degree, by diffusive
transport, through a concentration gradient. In the sediment, OCPs
associated with particles/organic matter can bury under sediment layers or
adsorb irreversibly and persist for decades (Doody 2002), metabolize by
microbiological or chemical activity, or become secondary sources of
contamination by resuspension or diffusion into the water column, either
naturally, i.e., abiotic disturbances or bioturbation (action of benthic
organisms), or anthropic, as occurred during dredging tasks.
In this compartment, as in the water column, OCPs are distributed
between the dissolved and particulate fractions. This partitioning is largely
regulated by the interaction of the compound with dissolved organic matter
(DOM) or sedimentary organic matter (associated with sediment particles;
SOM). Since the KOW and KOC of OCPs are in the high range, normally,
under the same environmental conditions, their sedimentary levels are
directly correlated to the content of SOM. However, sometimes, this
relationship fails because the SOM is heterogeneous, varying the absorption
18 Lautaro Girones, Pilar Palacios, Ana Laura Oliva et al.

capacity of OCPs from the sediment. Thus, two different types of SOM can
be physically and chemically differentiated: the amorphous or “soft” domain
and the condensed, “hard”, or vitreous domain (Weber et al. 1992). The first
is the dominant form of SOM and comprises mainly humic and fulvic
substances (Xiao et al. 2004). Furthermore, it has a low sorption capacity of
OCPs (and other chemicals) because it has linear sorption isotherms and
relatively fast sorption and desorption rates, with little or no difference
between both rates (e.g., Weber et al. 1992; Xiao et al. 2004). Instead, the
condensed domain is a minor part of the SOM, which is formed as a
consequence of the geological and thermal alteration of the amorphous
domain, and comprises mainly kerogen, soot, charcoal, black carbon (BC),
and humic acids in the vitreous form (Xiao et al. 2004). They are more
structured forms, with higher H/O ratio, higher aromaticity, and greater
sorption capacity due to presenting non-linear sorption isotherms, slow
sorption and desorption rates, and sorption-desorption hysteresis, i.e., OCPs
are trapped and retained (in some cases irreversibly) in micropores of
condensed organic matter that can be deformed leading to different sorption
and desorption isotherms (Weber et al. 1992, 1998; Xiao et al. 2004). This
sorption/ desorption kinetics plays an important role in the environment
since they regulate the exchange of contaminants between the dissolved and
particulate fractions (Lasaga 2014), hence, influence their bioavailability.
Consequently, according to the bioavailability of OCPs, three fractions can
be established: immediately available in the dissolved fraction; potentially
available, associated with DOM and the amorphous domain of the SOM;
and the little or not available fraction, associated with the condensed domain
of the SOM (Figure 3).
However, although the sediment sorption capacity is essential, other
factors influence the OCPs bioavailability in sediments such as the nature
and properties of the compounds, including KOW and molecular size
(Lyytikäinen et al. 2003), environmental conditions such as temperature, pH,
salinity, and bulk density (Akkanen and Kukkonen 2001), and age of the
OCPs in contact with the sediment, which increases the importance of the
unavailable fractions (Reichenberg and Mayer 2006).
Organochlorine Pesticides (OCPs) in Coastal Marine Environments 19

Figure 3. Schematic representation of the main phases and domains of geosorbents in


sediments in the aquatic environment.

In addition to sorption processes, most of the OCPs degradation occurs


in sediments, either by microbial or chemical action. Chemical degradation
occurs by photolysis (in the photic zones of the sediment), hydrolysis,
oxidation, and reduction (Andreu and Pico 2004). Meanwhile, the
microbiological degradation of pesticides occurs by consumption, as a
source of carbon and energy, by microorganisms generating structural
modification, generally by dehydrochlorination (Vollhardt and Schore
2000), and by cometabolism (microbial consortium), which generates a
series of consecutive transformations up to the total degradation of the
pesticide (Borja et al. 2005, Alexander 1981). Usually, the degradation rate
in the sediment is related to some key factors: the nature and properties of
the chemical compound, the existence and abundance of relevant
degradation agents, the bioavailability of the compounds (De Weert et al.
2008; Harwood et al. 2012), and the prevailing environmental conditions
such as temperature, oxygen level, solar radiation, and pH (Kang and Kondo
2005; Ying and Kookana 2003).

Air
Atmospheric transport is one of the main ways of pollutant dispersion
(Takeoka et al. 1991) and is the main pollution source in the polar regions
20 Lautaro Girones, Pilar Palacios, Ana Laura Oliva et al.

and oceanic environments (Bacon et al. 1992; Ono et al. 1987). Due to the
temperature gradient and consequently the KAW gradient, OCPs tend to
volatilize in low latitude regions, enter atmospheric circulation cells, and
transport to high latitudes, where they tend to condense and incorporate into
soil and water bodies. This phenomenon is known as global distillation and
may be responsible for the high concentrations of some OCPs in temperate
and polar regions (Simonich and Hites 1995). OCPs with low molecular
weight and high vapor pressure, such as hexachlorobenzene (HCB) and
hexachlorocyclohexanes (HCH), are usually more effectively dispersed in
cells, instead, those with low pressure and large molecular sizes, such as
DDT or toxaphene, do not transport effectively to high latitudes (Iwata et al.
1994; Simonich and Hites 1995). However, the combination of the broad
global use, environmental persistence, and relatively high Henry’s law
constant of these OCPs, promotes their presence, generally associated with
biota or sediments, at high latitudes. In addition to global distillation,
successive steps of volatilization/deposition and transport of OCPs occur
throughout the world through so-called “grasshopping”; hence, they can
affect all environments and ecosystems (Jurado and Dachs 2008). These
processes influence the OCP levels in coastal waters, especially in remote
areas such as Antarctica (Wu et a. 2020), Patagonia Argentina
(Commendatore et al. 2015), and Arctic (Jin et al. 2017; Ma et al. 2015),
since the chemicals can be incorporated by water-air exchange in these areas
or in the soil, vegetation, and water of the influence drainage basins (Dachs
and Méjanelle 2010; Figure 2).

Biota
Marine organisms can be exposed to OCPs through different routes.
OCPs dissolved in the air can enter organisms through lung respiration.
Meanwhile, OCPs dissolved in water, a fraction considered bioavailable, can
enter organisms from ingested water or through external surfaces such as
gills or skin tissues. Moreover, potentially available particle-associated
OCPs (i.e., those associated with the amorphous domain of organic matter)
and organism-incorporated OCPs can enter the consuming organisms
through food intake and be incorporated from the intestine (Knezovich et al.
Organochlorine Pesticides (OCPs) in Coastal Marine Environments 21

1987). Generally, OCP levels in small organisms are regulated by the


equitable partition between body lipids and water (KOW). Instead, OCP
levels are better related to diet than to KOW and lipid content in consuming
organisms. The effect of diet is particularly important due to OCPs, being
lipophilic and persistent compounds, increase their concentration through
the trophic web; therefore, the concentration in top predators is usually
higher than in those organisms with low trophic levels (biomagnification),
reaching differences of up to 10,000 times greater (Kajiwara et al. 2004;
Kleivane et al. 2004; Tanabe et al. 1994). Likewise, OCP levels show great
interspecific and intraspecific variability, determined by the complexity of
chemical, biological, and ecological factors that influence diets, such as
habitat, feeding behavior, and digestion mechanisms, as well as the
metabolizing capacity, chemical lipophilicity, and molecular size (Belfroid
et al. 1996; Lyytikäinen et al. 2003; Weston et al. 2000).
After organisms assimilate them, the fate of OCPs in the body can be
complex: they can store, metabolize, or excrete them. Mainly, OCPs tend to
migrate towards lipid reserves due to their high KOW, and it is common to
find a concentration gradient gastrointestinal tract> liver or brain> kidney>
muscle (Bryan et al. 1987; Dang et al. 2016; Zhao et al. 2014). While
excretion through the urine is considered to be negligible, due to its low
solubility in water. In contrast, the removal of OCPs by lipid mobilization
in processes such as gonadal maturation, ovulation, pregnancy, or lactation
is remarkable (Aguilar 1987). In lipid mobilization, some OCPs remain in
the tissue, but others leave the tissue with the lipids (Aguilar 1987). This
explains the low residue concentrations in adult females of marine mammals
about adult males (Girones et al. 2020; Kajiwara et al. 2004). Another way
for removal OCPs is degradation, in which the organisms themselves
transform the chemical compound into metabolites, which are sometimes
the same or more harmful and persistent than the parent pesticide. This
process occurs in most organisms and the main metabolic pathway is
through the cytochrome P-450 system (CYP-450), which contains
hemiproteins with iron used in the oxidation of hydrophobic xenobiotic
compounds. Through a cytochrome P-450 reductase enzyme, the reduction
of Fe3 + to Fe2 + occurs, which attracts an oxygen molecule and oxidizes
22 Lautaro Girones, Pilar Palacios, Ana Laura Oliva et al.

the pollutant forming a hydroxyl group (hydroxylation), which makes the


molecule more hydrosoluble and allows is excreted through the urine
(Parkki et al. 1977). However, not all organisms have the same ability to
degrade and remove OCPs, this ability is based on biochemical detox
adaptations that would be mainly related to diet, for example, the
detoxification ability of herbivores is greater than that of carnivores because
they are frequently exposed to a greater number of natural toxins in their diet
(Focardi et al. 1988; Fossi et al. 1988).

TOXICITY

Wild Animal Toxicity

Organochlorine pesticides were designed to eliminate arthropods by


neurotoxic action, i.e., acting directly on the nervous system and causing
sensory disturbances to seizures (ATSDR 2002). The magnitude and nature
of this effect are determined partly by the way and concentration in which
the OCPs reaches the receptor sensitive to it. If the OCP concentrations in
the active site are too low, or if the pesticide has been metabolized to an
inactive form, no impact will be observed.
Exposure to high environmental concentrations of OCPs generates
harmful effects on the biota in the short and long term. The most notable
effect was the decrease in the population of some wild bird species
associated with agricultural sites with intensive use of DDT, where this
compound was associated with the thinning of the eggshells, and
consequently to their breakage and reproductive failure (Bitman et al. 1969;
Burnett et al. 2013).
However, what generated the most interest in the scientific community
were the effects that low OCP levels can produce on the reproduction and
development of non-target organisms. These chemicals can act as endocrine
disruptors (Petrovic et al. 2013; Sosa-Ferrera et al. 2013) because they can
interfere with endogenous chemical messengers such as hormones,
neurotransmitters, growth factors, and inhibitory substances, affecting direct
Organochlorine Pesticides (OCPs) in Coastal Marine Environments 23

development, control of homeostatic regulation and the function of these


systems (Colborn et al. 1993). This hormonal system alteration has been
linked to the increase in some types of neoplasms, malformations, and
reproductive system dysfunctions, and immune response failures (Diamanti-
Kandarakis et al. 2009). Its effects are more noticeable in embryos, fetuses,
and newborns, producing in many cases irreversible effects as a product of
delayed development and organization of the organism (Guillette et al. 1995;
Mori and Nagasawa 1988).
Due to the large number of chemical indicators present among the cells
of developing systems, there are numerous targets on which OCPs can act
as chemical messengers. Therefore, detecting the small effects they cause
and predicting developmental injuries or modifications is very difficult.
Moreover, there may be a long delay between exposure and effects, hence
the latter may not be expressed until the maturity of the individual. These
individuals may appear normal but often experience early death or infertility
as a result of exposure (Colborn and Smolen 1996). If the problem were to
spread, these alterations in individuals could have serious consequences on
population levels.

Human Toxicity

Where OCPs are still in use, dermal and aerial exposure is important,
for example in cases where DDT is used to control malaria (Van Dyk et al.
2010). Furthermore, in some places, the consumption of contaminated fish
and shellfish could be a source of human exposure to OCPs (Beard 2006).
Both sources of OCPs exposure mean that significant levels can still be
measured in serum, adipose tissue, or breast milk samples from populations
not occupationally exposed (Gajski 2012).
Exposure to OCPs, even at very low levels, is associated with short
gestational periods, low weight in newborns, and below-average head
circumference measurements (Jacobson and Jacobson 1993). Furthermore,
it can affect the fertility of the individual, especially if this exposure occurs
during prenatal periods (Sharpe and Skakkebaek 1993), and generate liver,
24 Lautaro Girones, Pilar Palacios, Ana Laura Oliva et al.

neurological, pulmonary, and cardiac problems (Furuya et al. 2005;


Nakanishi et al. 2005). Besides, some pesticides would have a genotoxic
(Canales-Aguirre et al. 2011) and/or carcinogenic capacity in humans, e.g.,
lindane is carcinogenic, DDT and dieldrin are probably carcinogenic, and
others such as HCHs, HCB, and chlordane are possibly carcinogenic,
according to IARC (IARC 2020).

CURRENT OCP LEVELS IN COASTAL SEDIMENTS

Literature Review and Information Processing

Scientific articles on OCPs in coastal sediments worldwide published in


recent years (2015-2020) were reviewed. A comprehensive search was
performed on the most common search engines using different word
combinations. The compounds reviewed were: DDTs (o,p′-DDE, p,p′-DDE,
o,p′-DDD, p,p′-DDD, o,p′-DDT, and p,p′-DDT); HCHs (α-HCH, β-HCH, γ-
HCH, and δ-HCH); endosulfans (α-endosulfan, β-endosulfan, and
endosulfan sulfate); heptachlor (heptachlor and heptachlor epoxide);
chlordanes (trans-chlordane, cis-chlordane, trans-nonachlor, and cis-
nonachlor); drins (aldrin, dieldrin, endrin, and endrin aldehyde); HCB;
mirex; and methoxychlor. Levels below the detection limit were replaced by
half the detection limit when necessary. Data analysis of OCP levels was
performed with ArcGIS 10.3 (Esri, 380 New York Street, CA 92373, USA)
and Microsoft Excel (ver. 2013, Microsoft, Redmond, WA, USA), and
concentrations were expressed as ng.g-1 dry weight (dw). Moreover, to
determine the ecotoxicological risk associated with OCPs in the sediments,
the mean levels of each site were compared with the Norwegian
Environmental Quality Classification System (NEQCS; Bakke et al. 2010;
Molvær et al. 1997) and the guidelines proposed by Long et al. in 1995 and
Macdonald et al. in 1996 (Table 2). NEQCS establishes five risk classes for
five ranges of OCP concentrations in coastal marine environments:
background (CI); no toxic effects (CII); toxic effects following chronic
exposure (CIII); toxic effects following short term exposure (CIV); severe
Organochlorine Pesticides (OCPs) in Coastal Marine Environments 25

acute toxic effects (CV). Meanwhile, the guidelines proposed by Long and
Macdonald are similar, they establish two limit values that define three
ranges according to the frequency of adverse effects occurring in biota:
rarely, occasionally, and frequently. Long et al. defined these limit values as
“effects range low” (ERL) and “effects range median” (ERM), while
Macdonald et al. defined them as “threshold effect level” (TEL) and
“probable effects level” (PEL; Table 2).

Results and Discussion

DDTs
The current environmental concentrations of DDTs were higher than
those of the other OCPs, between 3 and 20 times depending on the group of
compounds compared. The general mean for 70 reviewed coastal sites in the
world was 8.43 ng.g-1 (SD = 30.84) with a global median of 1.71 ng.g-1. The
global spatial distribution of DDTs in coastal sediments was highly variable
and was related to the proximity to the sources and the hydrodynamic
characteristics of each environment, with Africa and Asia being the
continents most affected by DDT pollution, which are regions where its use
has not been totally discontinued (Van den Berg et al. 2017; Figure 4). When
comparing the levels of DDT in the sediments with the international
guidelines on ecotoxicological risk, it was observed that in many places
these compounds would cause some damage to the biota (Table 3). In
Jiulong Jiang, China (Lv et al. 2020) and iSimangaliso Wetland Park, South
Africa (Buah-Kwofie and Humphries 2017) these levels were 209.23 ng.g-1
and 138.14 ng.g-1, respectively, and they could cause severe and frequent
adverse effects on the biota according to the guidelines proposed by Long et
al. (1995), Macdonald et al. (1996) and NEQCS. Moreover, the levels of
DDTs from other sites could generate damage to the biota occasionally
according to these guidelines (Table 3). Regarding the distribution of DDT
congeners, a general predominance of DDT metabolites was observed over
the original DDT, suggesting a historical input to the systems (Figure 4).
Meanwhile, the DDE/DDD ratio varied mainly according to the oxygen
26 Lautaro Girones, Pilar Palacios, Ana Laura Oliva et al.

conditions and the solar exposure of the evaluated sediments. In general, the
subtidal sediments showed a predominance of DDD and the intertidal
sediments showed a predominance of DDE. For example, the DDE/DDD
ratios found in mangrove sediments studied by Chen et al. (2020) and Mitra
et al. (2019) were much greater than 1. Instead, the DDE/DDD ratios found
in subtidal sediments studied by Akhil and Sujatha (2014), Oliva et al.
(unpublished), and Jin et al. (2017) were much lower than 1. However, in
some places such as the Brazilian continental shelf (Santos et al. 2020) and
Guanghai Bay (Haijun et al. 2019), where the sediments are permanently
submerged, the DDE/DDD ratios were close to 1. This demonstrates that the
prevalence of anaerobic or aerobic degradation depends not only on the
waterlogging condition, but also on other factors, such as the diffusion of
oxygen from the water column to the sediments, influenced by the content
of organic matter, particle size, and the predominant hydrodynamics.

Table 2. Guidelines on ecotoxicological risk for organochlorine


pesticides in marine sediments. Values expressed as ng.g-1

Compounds ERLa ERMa TELb PELb CIId CIIId CIVd CVd


p,p,-DDT 1 7 1.19 4.77
p,p’-DDE 2.2 27 2.07 374
p,p’-DDD 2 20 1.22 7.81
DDTs 1.58 46.1 3.89 51.7 0-15 15-165 165- >
1647 1647
γ-HCH 0.32 0.99
HCHs < 0.074- 0.74-9.8 > 9.80
0.074 0.74
Endosulfans < 0.073- 0.6-6 >6
0.073 0.6
Endrin 2.67c 62.4c
Dieldrin 0.02 8 0.72 4.3
Chlordane 0.5 6 2.26 4.79
Heptachlor 0.6c 2.74c
epoxide
HCB 0-17 17-61 61-610 > 610
a. Long et al. 1995; b. Macdonald et al. 1996; c. CCME 2020 (www.ccme.ca); d. NEQCS
Organochlorine Pesticides (OCPs) in Coastal Marine Environments 27

Figure 4. Spatial distribution and composition of the mean levels of DDTs in


coastal sediments.

HCHs
HCH levels in sediment were on average 3 times lower than those of
DDTs, with a general mean of 2.85 ng.g-1 (SD = 12.03) and a median of 0.41
ng.g-1. Even so, high concentrations were found in some places around the
world (Figure 5). The highest levels were found in iSimangaliso Wetland
Park, South Africa (Buah-Kwofie and Humphries 2017), followed by Sado
Estuary (Carvalho et al. 2009), Unguja Island, Tanzania (Mwevura et al.
2020), Guajará Bay, Brazil (Neves et al. 2018), the Yangtze Estuary, China
(Adeleye et al. 2016), and the Nile River Estuary, Egypt (Abbassy et al.
2018) with an average of 95.8, 15.8, 4.65, 4.05, 3.93, and 3.61 ng.g-1,
respectively.
Due to its high toxicity, HCHs in sediment could cause damage to the
biota in the short or long term in most of the sites analyzed in recent years
(Table 3) according to the Norwegian Environmental Quality Classification
System (NEQCS; Bakke et al. 2010; Molvær et al. 1997). The sites most
affected by HCHs were the iSimangaliso Wetland Park, South Africa (Buah-
Kwofie and Humphries 2017), and the Sado Estuary, Portugal (Carvalho et
al. 2009), where these compounds could generate severe damage to the biota
in the short term.
28 Lautaro Girones, Pilar Palacios, Ana Laura Oliva et al.

Figure 5. Spatial distribution and composition of the mean levels of HCHs in


coastal sediments.

In turn, the ecotoxicological risk associated with the current levels of the
γ-HCH isomer (lindane) in sediments according to the guideline proposed
by MacDonald et al. (1996) coincided with that of the HCHs and is also
shown in Table 3.
Meanwhile, the α-HCH/γ-HCH ratio, which determines the
predominant use of technical HCH when it is in the 3 and 7 range and of
lindane (γ-HCH) when it is <1, indicated a predominant use of lindane in the
most places (Figure 5). However, some sites in Africa, China, and the Arctic
(Buah-Kwofie and Humphries 2017; Jin et al. 2017; Lv et al. 2020; Ma et
al. 2015) showed indices higher than 3, indicating a predominant use of
technical HCH or at least fast and efficient atmospheric transport from
distant sources in progress (Ma et al. 2015).

Drins
The study of the other OCPs is much less extensive than that of HCHs
and DDTs. Aldrin, dieldrin, and endrin were analyzed in 62%, 72%, and
62% of the reviewed studies, respectively. These compounds, usually
grouped under the name of “drins”, were found in considerably lower
concentrations than DDTs and HCHs (Figure 6). The global mean and
median concentrations were 1.44 ng.g-1 and 0.05 ng.g-1 for aldrin, 3.13 ng.g-
1
and 0.02 ng.g-1 for dieldrin, and 3.65 ng.g-1 and 0.13 ng.g-1 for endrin.
However, some places presented levels that could pose a risk to the
Organochlorine Pesticides (OCPs) in Coastal Marine Environments 29

associated biota according to the guidelines suggested by Long et al. (1995)


and MacDonald et al. (1996) (Table 3). The mean levels of dieldrin in
Cochin Estuary, India (Akhil and Sujatha 2014), iSimangaliso Wetland
Park, South Africa (Buah-Kwofie and Humphries 2017), and Sado Estuary,
Portugal (Carvalho et al. 2009) could cause frequent adverse effects on the
biota according to both guidelines. The concentration of dieldrin in other
sites around the world could cause occasional adverse effects on biota (Table
3). Meanwhile, endrin levels would not cause adverse effects at the studied
sites, except in Cochin Estuary, India (Akhil and Sujatha 2014),
Isimangaliso Wetland Park, South Africa (Buah-Kwofie and Humphries
2017), and Island Unguja, Tanzania (Mwevura et al. 2020), where they could
cause occasional damage to the associated biota, according to the guideline
proposed by MacDonald et al. (1996).

Endosulfans
The two isomers of technical endosulfan (α and β) were poorly studied,
they were analyzed only in 55% of the reviewed studies, and endosulfan
sulfate, its main metabolite, was analyzed in less than 40% of the studies.
The global mean concentration of endosulfans was 3.75 ng.g-1, although
with widely dispersed values (SD = 15.8; median = 0.11 ng.g-1). The high
standard deviation was mainly generated by high endosulfan concentrations
at two sites: iSimangaliso Wetland Park, South Africa (Buah-Kwofie and
Humphries 2017), and the Cochin Estuary, India (Akhil and Sujatha 2014)
with averages of 93.5 ng.g-1 and 21.01 ng.g-1, respectively (Figure 7). These
levels could generate acute toxic effects on the associated biota according to
the NEQCS (Table 3). Furthermore, according to this guideline, the average
levels found in some estuaries in Egypt, Vietnam, China, Argentina, and
Portugal (Abbassy 2018; Carvalho et al. 2009; Chen et al. 2020; Lv et al.
2020; Oliva et al. unpublished; Tham et al. 2019) could cause damage to the
associated biota in the short or long term (Table 3).
30 Lautaro Girones, Pilar Palacios, Ana Laura Oliva et al.

Figure 6. Spatial distribution and composition of the mean levels of drins in


coastal sediments.

Regarding the distribution of congeners, a clear pattern was observed.


In intertidal sediments, endosulfan sulfate was predominated over parent
endosulfans (e.g., Chen et al. 2020; Lv et al. 2020) while in subtidal
sediments the parent endosulfans were predominated (e.g., Abbassy 2018;
Akhil and Sujatha 2014; Commendatore et al. 2018; Ma et al. 2015; Oliva
et al. unpublished). This would be explained by the oxygen level in the
sediments: under aerobic conditions, the parent endosulfan is easily oxidized
to endosulfan sulfate, while in anaerobic or low-oxygen conditions, small
amounts of this analyte are produced (Ghadiri and Rose 2001; Guerin 1999).
Besides, in coastal sediments, under unfavorable environmental conditions
for oxidative degradation, the recent use of technical endosulfan would
promote the prevalence of the parent endosulfan over endosulfan sulfate.
Meanwhile, the predominance of α or β isomers of endosulfan depended on
both the environmental conditions and the physicochemical properties of the
isomers and the composition of the technical endosulfan (i.e., 70% α-isomer
and 30% β-isomer). The β isomer is more resistant to environmental
degradation and is less volatile than the α isomer (Breysse et al., 2015; Rand
et al. 2010), which is why it is usually predominant in water, fish, and
aerobic sediments (Granados- Galván et al. 2015; Rand et al. 2010). This
pattern was observed in intertidal sediments in China (Chen et al. 2020; Lv
et al. 2020), but also in subtidal sediments of the Nile River estuary, Egypt
(Abbassy et al. 2018). The prevalence of α-isomer was observed in subtidal
Organochlorine Pesticides (OCPs) in Coastal Marine Environments 31

sediments of Svalbard, Norwegian Arctic (Ma et al. 2015), Bahia Blanca


Estuary, Argentina (Oliva et al. unpublished), Cochin Estuary, India (Akhil
and Sujatha 2014), and San Jorge Gulf, Argentina (Commendatore et al.
2015). This could be due to a recent entry of technical endosulfan into the
system or to the low capacity to degrade both isomers in the absence or
shortage of oxygen and/or low temperatures (Ghadiri and Rose 2001).

Other Organochlorine Pesticides


Heptachlor was analyzed in 57% of the studies. The current global mean
concentration was 2.25 ng.g-1 (SD = 7.61) and the median was 0.04 ng.g-1,
which were low values about the previously analyzed OCPs. However, the
mean concentrations of heptachlor epoxide found in iSimangaliso Wetland
Park, South Africa (28.60 ng.g-1) and Cochin Estuary, India (2.77 ng.g-1)
would cause frequent damage to the associated biota according to the
guideline proposed by Macdonald et al. (1996; Table 3). Regarding the
distribution of heptachlor congeners, it was reported in the literature that
heptachlor would transform into heptachlor epoxide in aerobic conditions
through enzymatic epoxidation (Pokethitiyook and Toemthip 2012).
However, a prevalence of this metabolite over parental heptachlor was not
observed in intertidal sediments, where the oxygen level would be higher
than in subtidal sediments. On the other hand, it should be taken into account
that under oxygen-deficient conditions heptachlor would be metabolized to
chlordane and 1-hydroxychlordene-2,3-epochloride chloride (Pokethitiyook
and Toemthip 2012), and these metabolites were generally not analyzed.
Consequently, the study of the parent heptachlor/metabolites ratio and its
relationship to environmental conditions was very limited.
Chlordanes were evaluated in only 43% of the reviewed studies. The
general mean levels were very low, with a mean of 0.18 ng.g-1 (SD = 0.58)
and a median of 0.07 ng.g-1. Among the sites for which values were reported,
the levels of this pesticide would only cause occasional damage to the biota
in Anadim, Guajara Bay, Brazil (Neves et al. 2018), according to the
guidelines proposed by Long et al. (1995) and Macdonald et al. (1996; Table
3). Regarding the distribution of congeners, cis-chlordane/trans-chlordane
ratio ranged between 0.7 and 1.6 (Commendatore et al. 2015; Jin et al. 2017;
32 Lautaro Girones, Pilar Palacios, Ana Laura Oliva et al.

Lv et al. 2020; Ma et al. 2015; SFEI 2014) and their main metabolite,
oxychlordane, was hardly studied.
HCB was analyzed only in 27% of the studies reviewed. The mean
levels (mean of 2.12 ng.g-1, SD = 4.18, and median of 0.18 ng.g-1) were
similar to those of endosulfans and heptachlors. The sites with the highest
HCB concentrations were Congo River estuary, Congo DR (Suami et al.
2020), Bahía Blanca Estuary, Argentina (Tombesi et al. 2018), and Rhone
River delta, France (Salvadó 2013), with means of 14.06, 6.36, and 2.12
ng.g-1, respectively. Even so and according to NEQCS, HCB levels in
sediment would be biota-safe at all sites reviewed.
Mirex was determined in only 17% of the studies reviewed, in which it
was presented at very low levels. The general mean concentration was 0.03
ng.g-1 (SD = 0.04) and the median was 0.01 ng.g-1. Meanwhile, for
methoxychlor, the frequency of analysis was 23% and the global mean was
1.43 ng.g-1 with high SD (1.92) and a median of 0.4 ng.g-1. Neither of these
two pesticides is included in any ecotoxicological classification systems
used in this chapter, hence, we could not determine if the levels found would
pose any risk to the associated biota.

Figure 7. Spatial distribution and composition of the mean levels of endosulfans in


coastal sediments.
Table 3. Ecotoxicological risk associated with organochlorine pesticides in sediments in marine environments
around the world according to guidelines proposed by Long et al. (L; 1995), Macdonald et al. (M; 1996),
CCME (C), and NEQCs (N). OCPs contemplated were: p,p’-DDT (DDT); p,p’-DDE (DDE); p,p’-DDD (DDD);
Sum of p,p’-DDT, p,p’-DDE, and p,p’-DDD (DDTs); lindane (γ-HCH); Sum of α, β, γ, and δ HCH (HCHs);
Sum of α and β endosulfans and endosulfan sulfate (Endos); Sum of cis and trans chlordane (Chlord); dieldrin;
heptachlor epoxide (Hepx); and HCB

DDT DDE DDD DDTs γ-HCH HCHs Endos Chlord Dieldrin Endrin Hepx HCB
Authors
L M L M L M L M N M N N L M L M C C N
South America
Bahía Blanca 0 0 0 0 0 0 0 0 0 2 2 1 - - 0 0 0 1 - Oliva et al.
Estuary, Argentina unpublished
Bahía Blanca 0 0 0 0 0 0 1 0 0 0 1 - - - - - - - 0 Tombesi et al.
Estuary, Argentina 2018
Samborombón Bay, - - - - - - 0’ 0’ 0’ - 1 1 0 0 0 0 - - - Díaz-Jaramillo
Argentina et al. 2018
Quequen River - - - - - - 0’ 0’ 0’ - 0 1 0 0 1 0 - - - Díaz-Jaramillo
Estuary, Argentina et al. 2018
Bahía Blanca - - - - - - 0’ 0’ 0’ - 0 1 0 0 1 0 - - - Díaz-Jaramillo
Estuary, Argentina et al. 2018
Mar Chiquita - - - - - - 0’ 0’ 0’ - 0 1 0 0 0 0 - - - Díaz-Jaramillo
CoastalLagoon, et al. 2018
Argentina
San Blas Bay, 0 0 0 0 - - 0 0 0 0 1 1 0 0 0 0 0 0 - Commendatore
Argentina et al. 2018
San Jorge Gulf, 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 Commendatore
Argentina et al. 2015
Santa Catarina (N), 0 0 0 0 0 0 0 0 0 - - - - - - - - - - Santos et al.
continental shelf, 2020
Brazil
Santa Catarina (S), 0 0 0 0 0 0 0 0 0 - - - - - - - - - - Santos et al.
continental shelf, 2020
Brazil
Table 3. (Continued)

DDT DDE DDD DDTs γ-HCH HCHs Endos Chlord Dieldrin Endrin Hepx HCB
Authors
L M L M L M L M N M N N L M L M C C N
Rio Grande do Sul, - - 0 0 - - 0 0 0 - - - - - - - - - - Santos et al.
continental shelf, 2020
Brazil
Anadim, Guajará - - - - - - 0’ 0’ 0’ - 2 - 1 1 - - - - - Neves et al.
Bay, Brazil 2018
Outerio, Guajará - - - - - - 0’ 0’ 0’ - 1 - 0 0 - - - - - Neves et al.
Bay, Brazil 2018
Babitonga Bay, 1 2 0 0 0 0 1 1 0 0 1 0 0 0 0 0 0 0 0 Rizzi et al.
Brazil 2017a
Paranaguá Estuary, - - - - - - 0 0 0 0 2 - 0 0 0 0 - - - Rizzi et al.
Brazil 2017b
Central and North America and the Arctic Ocean
Bering Sea, Arctic 0 0 0 0 0 0 0 0 0 0 1 - 0 0 - - - - - Jin et al. 2017
Chuckchi Sea, Arctic 0 0 0 0 0 0 0 0 0 0 1 - 0 0 - - - - - Jin et al. 2017
Jobos Bay, Puerto 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 - Huber 2018
Rico
Kongsfjorden, - - - - - - - - - 0 0 0 0 0 - - - - - Ma et al. 2015
Svalbard
San Francisco Bay, 1 1 0 0 0 0 1 1 0 0 0 - 0 0 1 0 0 0 0 SFEI 2014
US
Asia
Jiulong Jiang, China - - - - - - 2’ 2’ 2’ - 2 1 0 0 - - - - - Lv et al. 2020
Hangu, China - - - - - - 1’ 1’ 0’ - 1 1 0 0 - - - - - Lv et al. 2020
Dagu He, China - - - - - - 1’ 1’ 0’ - 1 1 0 0 - - - - - Lv et al. 2020
Zhu Jiang, China - - - - - - 1’ 1’ 0’ - 1 1 0 0 - - - - - Lv et al. 2020
Min Jiang, China - - - - - - 1’ 1’ 0’ - 1 1 0 0 - - - - - Lv et al. 2020
Chang Jiang, China - - - - - - 1’ 1’ 0’ - 1 1 0 0 - - - - - Lv et al. 2020
Daliao He, China - - - - - - 1’ 0’ 0’ - 1 0 0 0 - - - - - Lv et al. 2020
Dongzhai Gang, - - - - - - 1’ 0’ 0’ - 1 0 0 0 - - - - - Lv et al. 2020
China
DDT DDE DDD DDTs γ-HCH HCHs Endos Chlord Dieldrin Endrin Hepx HCB
Authors
L M L M L M L M N M N N L M L M C C N
Hangzhou Wan, - - - - - - 1’ 0’ 0’ - 1 0 0 0 - - - - - Lv et al. 2020
China
Yingluo Wan, China - - - - - - 1’ 0’ 0’ - 1 0 0 0 - - - - - Lv et al. 2020
Dongying, China - - - - - - 0’ 0’ 0’ - 1 0 0 0 - - - - - Lv et al. 2020
Yancheng, China - - - - - - 0’ 0’ 0’ - 1 0 0 0 - - - - - Lv et al. 2020
Beidaihe, China - - - - - - 0’ 0’ 0’ - 1 0 0 0 - - - - - Lv et al. 2020
Sishili Wan, China - - - - - - 0’ 0’ 0’ - 1 0 0 0 - - - - - Lv et al. 2020
Intertidal sediments, 2 2 1 1 1 1 1 1 1 0 1 1 0 0 0 0 0 0 - Lv et al. 2020
China
Zhang River Estuary, 0 0 0 0 0 0 0’ 0’ 0’ 0 1 2 - - 1 0 0 0 - Chen et al.
China 2020
Guanghai Bay, China 0 0 0 0 0 0 0 0 0 0 1 - - - 1 0 0 0 0 Haijun et al.
2019
Yangtze Estuary, 0 0 0 0 - - 0’ 0’ 0’ 2 2 - - - - - - - - Adeleye et al.
China 2016
Hangzhou Bay, 0 0 0 0 - - 0’ 0’ 0’ 2 2 - - - - - - - - Adeleye et al.
China 2016
Continental Margin 0 0 0 0 - - 0’ 0’ 0’ 2 2 - - - - - - - - Adeleye et al.
East China Sea 2016
Hooghly estuary, 0 0 0 0 0 0 1 0 0 0 1 - - - - - - - 0 Mitra et al.
India 2019
Cochin Estuary, India 2 2 1 1 1 1 1 1 1 - 2 3 - - 2 2 1 2 - Akhil and
Sujatha 2014
Nhat Le Estuary, - - - - - - 1 1 0 - 2 2 - - - - - - - Tham et al.
Vietnam 2019
Cua Hoi Estuary, - - - - - - 1 1 0 - 2 2 - - - - - - - Tham et al.
Vietnam 2019
Han River Estuary, - - - - - - 1 0 0 - 2 2 - - - - - - - Tham et al.
Vietnam 2019
Lang Co Lagoon, - - - - - - 1 0 0 - 2 2 - - - - - - - Tham et al.
Vietnam 2019
Cua Dai Estuary, - - - - - - 1 0 0 - 2 2 - - - - - - - Tham et al.
Vietnam 2019
Table 3. (Continued)

DDT DDE DDD DDTs γ-HCH HCHs Endos Chlord Dieldrin Endrin Hepx HCB
Authors
L M L M L M L M N M N N L M L M C C N
Cua Viet Estuary, - - - - - - 1 0 0 - 2 2 - - - - - - - Tham et al.
Vietnam 2019
Vientam estuaries, - - - - - - 1 1 0 - 2 2 - - - - - - - Tham et al.
Vietnam 2019
Cua Dai estuary, - - - - - - 1 0 0 - 2 - - - 1 0 - - - Nguyen et al.
Vietnam 2019
Mediterranea Sea and Europe
Nile River Estuary, 0 0 0 0 0 0 1’ 0’ 0’ 1 2 2 - - 0 0 0 1 - Abbassy 2018
Egypt
Rhone delta, France - - - - - - 1’ 1’ 0’ - 2 - - - - - - - 0 Salvadó 2013
Tiber River Estuary, - - - - - - - - - - 1 - - - - - - - - Montuori et al.
Italy 2016
Southern portugal, 1 1 1 1 0 1 1 1 0 2 3 2 - - 2 2 0 1 - Carvalho et al.
Portugal 2009
Northern portugal, 1 1 0 0 0 0 1 1 0 2 2 2 - - 1 1 0 0 - Carvalho et al.
Portugal 2009
Edremit Bay, Aegean 0 0 0 0 0 0 0 0 0 0 0 - 0 0 0 0 0 0 - Darilmaz et al.
Sea, Turkey 2019
Sub-saharanafrica
Congo River estuary, 0 0 0 0 0 1 1 0 0 0 0 0 0 0 0 0 0 0 0 Suami et al.
Congo DR 2020
iSimangaliso 2 2 2 1 2 2 2 2 1 2 3 3 - - 2 2 1 2 - Buah-Kwofie
Wetland Park, South and Humphries
Africa 2017
Unguja Island, 0 0 1 1 0 0 1 1 0 2 2 - - - 1 1 1 - - Mwevura et al.
Tanzania 2020
Long et al. 1995 (L): Conc.(concentration) < ERL (0; rarely adverse effects in biota), ERL< Conc.< ERM (1; occasionally adverse effects in biota), Conc. > ERM (2; frequently adverse effects in biota);
Macdonald et al. 1996 (M) and CCME (C): Conc. < TEL (0; rarely adverse effects in biota), TEL < Conc. < PEL (1; occasionally adverse effects in biota), Conc. > PEL (2; frequently adverse
effects in biota); NECQS (N): CII (0; no toxic effects), CIII (1; toxic effects following chronic exposure), CIV (2; toxic effects following short term exposure), CV (3; severe acute toxic effects).
Lautaro Girones, Pilar Palacios, Ana Laura Oliva et al. 37

CONCLUSION

Although it seems that the problem associated with the production and
use of organochlorine pesticides has disappeared due to the worldwide
restrictions, they remain as one of the most important pollutants for both the
environment and humans. At almost all the coastal sites where were recently
evaluated, OCP levels showed detectable concentrations of at least one
congener. In some cases, mainly in sub-Saharan Africa and Southeast Asia,
these concentrations were high and would pose a risk to the biota associated
with these environments.
DDTs were the most abundant legacy POP in marine coastal sediments,
3 times more abundant than HCHs and much more abundant than the rest of
the OCP. However, from an environmental point of view, other pesticides
were shown to be more dangerous due to their greater ecotoxicity.
Regarding the environmental fate and behavior of OCPs, the factors
influencing them were exhaustively described from the literature analysis.
This information was then used to assess current levels of OCPs in the
world’s coastal sediments in various studies. We observe that the
environmental behavior of these compounds is very complex and depends
fundamentally on the intrinsic characteristics of each compound and the
environment.
Parent pesticides were found at almost all the sites studied, which could
represent a recent input into the system or poor system capacity to degrade
them. This was observed mainly in subtidal sediments, which would have
low oxygen content and little or no light exposure, i.e., unfavorable
conditions for the aerobic degradation of the OCPs, which is the main route
of degradation in the environment. Moreover, this phenomenon was more
noticeable in cold or temperate environments.
The predominance of each metabolite and parent isomer varied
according to the prevailing environmental conditions. In intertidal
sediments, the metabolites and isomers typical of oxygenated environments
predominated, i.e., DDE, endosulfan sulfate, heptachlor epoxide, β-HCH,
and β-endosulfan. Instead, metabolites typical of anaerobic environments
38 Lautaro Girones, Pilar Palacios, Ana Laura Oliva et al.

such as DDD and the majority isomers of the technical mixtures (α-
endosulfan, lindane, and α-HCH) predominated in subtidal sediments.
Finally, we must highlight the need to sustain permanent monitoring
networks for these legacy pollutants, with a focus on non-surveyed regions
and potentially polluted areas such as African and Asian coastal wetlands.

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freshwater fishes: a case study performed in Poyang Lake, China’s
largest lake. Environmental Science and Pollution Research, 21(14),
8740-8749. DOI: https://doi.org/10.1007/s11356-014-2805-z.

BIOGRAPHICAL SKETCH

Name: Lautaro Girones


Affiliation: Instituto Argentino de Oceanografía (IADO) - Consejo
Nacional de Investigaciones Científicas y Técnicas (CONICET) and
Universidad Nacional del Sur (UNS) -, Bahía Blanca, Provincia de Buenos
Aires, Argentina.
Education: I have a degree in Environmental Sciences from the
Universidad Nacional de Avellaneda (UNDAV), Avellaneda, Province of
Buenos Aires, Argentina, and I am a Ph.D. student from the Universidad
54 Lautaro Girones, Pilar Palacios, Ana Laura Oliva et al.

Nacional del Sur (UNS), Bahía Blanca, Province of Buenos Aires,


Argentina. Besides, I have taken more than 15 graduate courses.
Business Address: Instituto Argentino de Oceanografía. Florida 8000
(Camino La Carrindanga km 7,5), Complejo CCT CONICET Bahía Blanca
| Edificio E1, B8000FWB Bahía Blanca | Argentina
Research and Professional Experience:
Since April 2017 I have been a CONICET doctoral fellow developing
my research activities at the Persistent Organic Pollutants Laboratory of the
Instituto Argentino de Oceanografía (IADO), in Bahía Blanca, Argentina.
My directors are Dr. Andres Hugo Arias and Dr. Jorge Eduardo
Marcovecchio. I specialize in the study of Persistent Organic Pollutants such
as organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs),
chlorinated paraffins (SCCPs and MCCPs), and polycyclic aromatic
hydrocarbons (PAHs) in marine and continental aquatic environments. I
have participated in several research projects, including research stays
abroad, some of which have already been published in international
scientific journals or will be published in the coming years. Among them,
the study of pollution by POPs and their behavior and environmental fate in
the Southwest of Buenos Aires stands out, analyzing both rivers and the
Bahía Blanca Estuary, through the use of abiotic (e.g., sediments and water)
and biotic matrices (e.g., snails, mussels, and fish). Besides, I also participate
in the study of the river discharges impacts on the marine benthic community
of the Province of Buenos Aires; the role of coastal wetland plants in the
biogeochemical cycle of POPs; and the occurrence and environmental
behavior of POPs in the Argentine continental shelf, among others.
Professional Appointments:
Honors:
Publications from the Last 3 Years:
Girones, L., Arias, A. H., Oliva, A. L., Recabarren-Villalon, T. &
Marcovecchio, J. E. (2020). Occurrence and spatial distribution of
organochlorine pesticides in the southwest Buenos Aires using the
freshwater snail Chilina parchappii as environmental biomonitor.
Regional Studies in Marine Science., Volume 33, 10089.
https://doi.org/10.1016/j.rsma.2019.100898.
Organochlorine Pesticides (OCPs) in Coastal Marine Environments 55

Girones, L., Arias, A. H. & Marcovecchio, J. E. (2019). Distribution of


organochlorine pesticides (OCs) in coastal sediments of Latin America.
JAINA coasts and seas in the face of climate change. Volume 1, 2.
Girones, L., Oliva, A. L., Marcovecchio, J. E. & Arias, A. H. (2020). Spatial
distribution and ecological risk assessment of residual organochlorine
pesticides (OCPs) in South American marine environments. Current
Environmental Health Reports., Volume 7, 147-160.
https://doi.org/10.1007/s40572-020-00272-7.
Negrin, V. L., Girones, L. & Serra, A. V. (2019). Eco-friendly strategies of
remediation in the marine system: bioremediation and
phytoremediation. In: Coastal and Deep Ocean Pollution 1st Edition.
Eds: Andres H. Arias and Sandra E. Botte. CRC Press/ Taylor & Francis
Group. ISBN-10: 1138569399; ISBN-13: 978-1138569393. 370 pp.
Oliva, A. L., Ronda, A. C., Girones, L., Orazi, M. M., Recabarren-Villalón,
T., Marcovecchio, J. E. & Arias, A. H. (2019). Polycyclic Aromatic
Hydrocarbons: sources, occurrence, levels, distribution and
ecotoxicological fate at coastal and Deep Ocean. In: Coastal and Deep
Ocean Pollution 1st Edition. Eds: Andres H. Arias and Sandra E. Botte.
CRC Press/ Taylor & Francis Group. ISBN-10: 1138569399; ISBN-13:
978-1138569393. 370 pp.
Palacios, P., Girones, L., Vitale, C. A., Arias, A. H.. Chapter 2. Occurrence,
Behavior and Ecotoxicity of Organophosphorus Pesticides (OPPs) in
Marine Environments: A Review. In: Marine Environments: Diversity,
Threats and Conservation. Ed: Lina Charles. Nova Science Publishers.
ISBN: 978-1-53618-874-5
Girones, L., Palacios, P., Oliva, A. L., Marcovecchio, J. E., Arias, A. H..
Chapter 3. Organochlorine Pesticides (OCPs) in Coastal Marine
Environments: Levels, Fate, Behavior, and Effects on Biota. In: Marine
Environments: Diversity, Threats and Conservation. Ed: Lina Charles.
Nova Science Publishers. ISBN: 978-1-53618-874-5
56 Lautaro Girones, Pilar Palacios, Ana Laura Oliva et al.

Name: Dr. Andres H Arias


Affiliation:

 Instituto Argentino de Oceanografía (IADO) - Consejo Nacional de


Investigaciones Científicas y Técnicas (CONICET) and
Universidad Nacional del Sur (UNS) -, Bahía Blanca, Provincia de
Buenos Aires, Argentina.
 Analytical Chemistry Area of the Chemistry Department of the
National South University (Argentina)

Education:

 PhD Biological Sciences Marine Environmental Chemistry: water,


soil and organism. Biogeochemistry. Environment Pollution and
Monitoring. National South University, Argentina. Awarded with
honour (10/10)
 BIOCHEMISTRY Sciences (Analytical Chemistry and
Environmental Sciences Degree) at National South University,
Argentina. Awarded with Honours. First award in qualifications
9.13/10

Business Address: Instituto Argentino de Oceanografía. Florida 8000


(Camino La Carrindanga km 7,5), Complejo CCT CONICET Bahía Blanca
| Edificio E1, B8000FWB Bahía Blanca | Argentina
Organochlorine Pesticides (OCPs) in Coastal Marine Environments 57

Research and Professional Experience: My area of expertise falls


between marine biogeochemistry and ocean monitoring, focusing in the
pollution of the marine and coastal environments: Persistent Organic
Compounds/Environmental Pollution Monitoring and Assessment. Plastics
and Microplastics in the aquatic environment. Atmospheric transport of
POPs to the coastal environments. Dry/Wet Deposition. Bioaccumulation
and Biomagnification of POPs. Top predators.
My main interests are to explore Persistent Organic Pollutants (POPs)
and microplastic dynamics occurrence and bioaccumulation in marine and
freshwater environments, the understanding of POPs movement through the
trophic web, exploring POPs sources, origin and age of inputs PAHs,
PBDEs, PCBs, OCs, OPs, emerging pollutants and microplastics in the
marine/freshwater environment.
Professional Appointments: At present, researcher at the Argentinean
Institute of Oceanography -IADO- (National Council of Scientific and
Technological Research, CONICET, Argentina) at the Marine Chemistry
Division. He is also Head of Laboratory (Teaching Position, permanent) at
the Analytical Chemistry Area of the Chemistry Department of the National
South University (Argentina). In addition, UNEP representative at Scientific
Advisory Comitee Microplastics and Marine Litter and representative of
Argentina at the GESAMP WG40. Presently, member of the Directive
Council Board of the Argentinean Institute of Oceanography (CONICET).
He has performed posdoc at the University of Lille-1, Lille, France (CNRS)
and UNAM, Mexico (CONACyT).
Honors:
Awarded with the WIENER LAB Foundation prize (academic award),
to the best overall qualification average of the year (2003) of the
Biochemistry University Degree.
First award for a conference paper at the VII Jornadas Chilenas de Física
y Química Ambiental (Concepción; Chile, 2011).
First award on conference paper in marine environments (Environment
and Argentina, 2015).
Has been awarded with several grants (PICES, Erasmus Mundus,
Matsumae, IMBER ClimEco, etc)
58 Lautaro Girones, Pilar Palacios, Ana Laura Oliva et al.

Publications from the Last 3 Years (2020-2018):


Journal Articles from the last three years

[1] Alfonso, MB; Scordo, F; Seitz, C; Manstretta, GMM; Ronda, AC;


Arias, AH; Piccolo, MC. (2020). First evidence of microplastics in
nine lakes across Patagonia (South America). Science of The Total
Environment, 139385.
[2] Girones, L; Oliva, AL; Marcovecchio, JE; & Arias, AH. (2020).
Spatial Distribution and Ecological Risk Assessment of Residual
Organochlorine Pesticides (OCPs) in South American Marine
Environments. Current Environmental Health Reports, 1-14.
[3] Pozo, Karla; Urbina, Williams; Gómez, Victoria; Torres, Mariett;
Nuñez, Dariela; P?Ibylová, Petra;Audy, Ond?EJ; Clarke, Bradley;
Arias, Andrés; Tombesi, Norma; Guida, Yago; Klánová, Jana.
Persistent organic pollutants sorbed in plastic resin pellet &mdash;
&ldquo;Nurdles&rdquo; from coastal areas of Central Chile. Marine
Pollution Bulletin: Pergamon-Elsevier Science Ltd., 2020 vol. 151, n°.
p - . issn 0025- 326X.
[4] Das, Shagnika; Arias, Andres HUGO; Cheng, Jing-O; Souissi, Sami;
Hwang, Jiang-Shiou; KO, Fung-Chi. Occurrence and distribution of
anthropogenic persistent organic pollutants in coastal sediments and
mud shrimps from the wetland of central Taiwan. Plos One.: Public
Library Science., 2020 vol.15 n°1. p - . issn 1932-6203.
[5] Alfonso, MB; Arias, HA; Piccolo, MC. Microplastics integrating the
zooplanktonic fraction in a saline lake of Argentina: influence of water
management. Environmental Monitoring and Assessment.: Springer.
2020, vol. 192, n°. p - . issn 0167-6369.
[6] Andrés Hugo Arias; Ronda, Ana Carolina; Oliva, Ana Laura; Jorge
E. Marcovecchio. Evidence of Microplastic Ingestion by Fish from the
Bahía Blanca Estuary in Argentina, South America. Bulletin OF
Environmental Contamination and Toxicology.: Springer., 2019, vol.
n°. p - . issn 0007-4861.
[7] Quintas, Pamela Y; Alvarez, Mónica B; Andrés H. Arias; Garrido,
Mariano; Jorge E. Marcovecchio. Spatiotemporal distribution of
Organochlorine Pesticides (OCPs) in Coastal Marine Environments 59

organotin compounds in the coastal water of the Bahía Blanca estuary


(Argentina). Environmental Science and Pollution Research.
Heidelberg: Springer Heidelberg., 2019, vol. n°. p - .issn 0944-1344.
[8] Quintas, Pamela Y; Fernandez Eleonora; Carla V. Spetter; Andres H
Arias; Garrido, Mariano; Jorge E. Marcovecchio. Preliminary studies
about the role of physicochemical parameters on the
organotincompounds dynamic in a South American Estuary (Bahía
Blanca, Argentina). Environmental Monitoring and Assessment.
Berlin: Springer. 2019 vol. n°. p - . issn 0167-6369.
[9] Oliva, Ana L; La Colla, Noelia S; Arias, Andrés H; Botté, Sandra E;
Perillo, Gerardo ME; Piccolo, M. Cintia. First records of polycyclic
aromatic hydrocarbons and metals in sediments from a shallow lake in
the Pampean&ndash; Patagonian region (Argentina). Marine and
Freshwater Research.: Csiro Publishing., 2019, vol. n°. p - . issn 1323-
1650.
[10] Recabarrén-Villalón, Tatiana; Ronda, Ana C; Arias, Andrés H.
Polycyclic aromatic hydrocarbons levels and potential biomarkers in a
native South American marine fish. Regional Studies in Marine
Science.: Elsevier BV., 2019, vol. n°. p - . issn 2352-4855.
[11] Orazi, Melina M; Arias, Andrés H; Oliva, Ana L; Ronda, Ana C;
Marcovecchio, Jorge E. Characterization of atmospheric and soil
polycyclic aromatic hydrocarbons and evaluation of air-soil
relationship in the Southwest of Buenos Aires province (Argentina).
Chemosphere.: Pergamon-Elsevier Science Ltd. 2019, vol. n°. p - . issn
0045-6535.
[12] Ronda, Ana C; Arias, Andrés .; Oliva, Ana L; Marcovecchio, Jorge
E. Synthetic microfibers in marine sediments and surface seawater
from the Argentinean continental shelf and a Marine Protected Area.
Marine Pollution Bulletin.: Pergamon-Elsevier Science Ltd., 2019 vol.
149, n°. p - . issn 0025-326X.
[13] Girones, Lautaro; Arias, Andrés H; Oliva, Ana L; Recabarren-
Villalon, Tatiana; Marcovecchio, Jorge E. Occurrence and spatial
distribution of organochlorine pesticides in the southwest Buenos
Aires using the freshwater snail Chilina parchappii as environmental
60 Lautaro Girones, Pilar Palacios, Ana Laura Oliva et al.

biomonitor. Regional Studies in Marine Science.: Elsevier., 2019, vol.


n°. p - . issn 2352-4855.
[14] Quintas, Pamela Y; Oliva, Ana L; Alvarez, Mónica B; Arias, Andres
H; Domini, Claudia E; Garrido, Mariano; Marcovecchio, Jorge E. Fast
and Feasible Ultrasound-Assisted Pretreatment for the Determination
of Organotin Compounds in Environmental Samples. Archives of
Environmental Contamination and Toxicology.: Springer., 2018, vol.
n°. p - . issn 0090-4341.
[15] Tombesi, Norma; Pozo, Karla; Arias, Andrés; Alvarez, Mónica;
Pribylova, Petra; Audy, Ondrej; Klánová, Jana. Records of
organochlorine pesticides in soils and sediments on the southwest of
Buenos Aires Province, Argentina. Environmental Earth Sciences.
Heidelberg: Springer Berlin Heidelberg., 2018, vol. 77, n°11. p - . issn
1866-6280. eissn 1866-6299.
[16] Vitale, Alejandro J; Perillo, Gerardo ME; Genchi, Sibila A; Arias,
Andrés H; Piccolo, María Cintia. Low-cost monitoring buoys network
tracking biogeochemical changes in lakes and marine environments; a
regional case study. Pure and Applied Chemistry.: Int Union Pure
Applied Chemistry., 2018, vol. 0, n° 0. p - . issn 0033-4545.
[17] Ronda, Ana Carolina; Oliva, Ana Laura; Andres H Arias; Orazi,
Melina Mirta; Jorge E. Marcovecchio. Biomarker responses to
polycyclic aromatic hydrocarbons in the native fish Ramnogaster
arcuata, South America. International Journal of Environmental
Research.: Univ Tehran., 2018, vol. n°. p - . issn 1735-6865.

Books:

Title: “Coastal and Deep Ocean Pollution”. Editors: Andrés H. Arias &
Sandra E. Botte-Taylor & Francis-/CRC Press, 2020.
https://www.crcpress.com/Coastal-and-Deep-Ocean-Pollution/Arias-
Botte/p/book/9781138569393

Book Chapters
Organochlorine Pesticides (OCPs) in Coastal Marine Environments 61

[1] The Northern Argentine Sea. Marcovechio JE, De Marco S, Gavio,


Narvarte M, Fiori S, Gerpe M, Rodriguez D, Abbate C., La Colla N,
Oliva AL, Zalva S., Bazterrica MC, Guinder V, Spetter V, Fernandes
M, Arias AH, Botte S. En: World Seas: An environmental Evaluation.
Volume I Europe America and West Africa, Charles Sheppard Ed.,
ISBN 978-0-12-805068-2.2019.
[2] Vulnerabilidad de ecosistemas marino costeros Sudamericanos a
Contaminantes Orgánicos Persistentes: panorama actual e histórico.
Arias AH, Oliva AL, Ronda AC, OraziMM, Marcovecchio JM. En:
Vulnerabilidad de las Zonas Costeras ante el Cambio Climático, III
Ed. ISBN 9786077887300. UNAM-ICMYT-UCampeche.2019
[3] “LA ZONA COSTERA DE ARGENTINA EN UN ESCENARIO DE
CAMBIOS CLIMATICOS: VULNERABILIDAD, PERSPECTIVAS
Y TENDENCIAS”, Marcovecchio JE, La Colla NS, Vallina N, De
Marco S., Hidalgo F, Arias AH, Spetter CV. En:
VULNERABILIDAD DE LAS ZONAS COSTERAS DE
LATINOAMÉRICA AL CAMBIO CLIMÁTICO".ISBN
9786077887300. UNAM-ICMYT-UCampeche. Mexico.2018.

Conference Papers

[1] Arias Andrés; Ronda, Ana Carolina; Oliva, AL; Orazi, Melina Mirta;
Girones, Lautaro; Recabarrén-Villalón, Tatiana; Norma Tombesi;
Karla Pozo; JE. Marcovecchio. South Atlantic Environmental
Monitoring: POPs Assessment in Several Marine ECOSYSTEM
Matrix (Argentina). Japón. Kyoto. 2019. Libro. Artículo Breve.
Congreso. dioxins 2019. dioxins.org
[2] ANDRES H ARIAS; KARLA POZO; ALVAREZ, MÓNICA;
NORMA TOMBESI. HIDROCARBUROS AROMÁTICOS
POLICICLICOS (HAPs) EN AIRE DE LA CIUDAD DE BAHIA
BLANCA Y REGIÓN DEL SUDOESTE BONAERENSE. Argentina.
La Plata. 2019. Libro. Artículo Breve. Congreso. V Reunión Argentina
62 Lautaro Girones, Pilar Palacios, Ana Laura Oliva et al.

de Geoquímica de la
SUPERFICIE.CONICET/UNLP/CIG/CEQUINOR.
[3] Andrés H. Arias; Ronda, Ana C; Oliva, Ana Laura; Recabarrén-
Villalón, Tatiana; Girones, LAUTARO; Orazi, Melina Mirta; Blasina,
Gabriela E; Lopez Cazorla Andrea; N. Tombesi; Jorge E.
Marcovecchio. Detección Y Niveles de Hidrocarburos Aromáticos
Policíclicos (HAPS) en Cuatro Especies de PECES DEL ESTUARIO
de Bahía Blan¬CA, Argentina. Argentina. La Plata. 2019. Libro.
Artículo Breve. Congreso. V Reunión Argentina de Geoquímica de la
Superficie.CONICET/UNLP/CIG/CEQUINOR.
[4] Quintas, Pamela; Alvarez, Mónica; Andres H Arias; Domini, Claudia;
Garrido, Mariano; Jorge Marcovecchio. Evaluación integral de la
distribución compuestos organoestánnicos en el estuario de Bahía
Blanca. Uso de técnicas quimiométricas para la visualización e
interpretación de datos. Argentina. Santa Rosa. 2019. Libro. Artículo
Breve. Congreso. 10mo Congreso Argentino de Química Analitica.
Universidad Nacional de La Pampa.
[5] Andres H Arias; Pozo, Karla; Alvarez, Mónica B.; Norma Tombesi.
Polycyclic aromatic hydrocarbons (PAHs) in surficial soils on the
southwest of Buenos Aires province. Argentina. Tandil. 2018. Libro.
Artículo Completo. Jornada. II Jornadas Internacionales y IV Jornadas
Nacionales de Ambiente 17-19 de Octubre de 2018, UNICEN
TANDIL, Argentina. UNICEN.
[6] Recabarren Tatiana; Ronda, Ana Carolina; Abasto, Benjamin; Andres
H Arias. Relación entre el estrés oxidativo y parámetros biológicos en
Bracchidontes rodriguezzi del estuario de Bahía Blanca. Argentina.
Buenos Aires. 2018. Libro. Artículo Breve. Jornada. X Jornadas
NAcionales de Ciencias del Mar. UBA FCEyN.
[7] Girones Lautaro; Oliva, Ana Laura; Carbone Elisabeth; Lopez,
Gustavo; Jorge E. Marcovecchio; Andres H Arias. Distribución de
pesticidas organoclorados en caracoles dulceacuícolas en una cuenca
del suroeste bonaerense y su relación con el uso del suelo. Argentina.
San Luis. 2018. Libro. Artículo Breve. Congreso. VII Congreso
Argentino de la SETAC. SETAC Argentina.
Organochlorine Pesticides (OCPs) in Coastal Marine Environments 63

[8] Orazi, Melina Mirta; Andrés H. Arias; Girones Lautaro; Jorge


Marcovecchio. Soil-Air exchange for Polycyclic Aromatic
Hydrocarbons (PAHs) from the southwest of Buenos Aires Province
(Argentina). Argentina. San Luis. 2018. Libro. Artículo Breve.
Congreso. VII Congreso Argentino de la SETAC. SETAC Argentina.
[9] Recabarren Tatiana; Ronda, Ana Carolina; Andres H Arias. Relación
entre el estrés oxidativo y parámetros biológicos en Chilina parchapii
del Arroyo Napostá Grande. Argentina. San Luis., 2018. Libro.
Artículo Breve. Congreso. VII Congreso Argentino de la SETAC.
SETAC Argentina.
[10] Ronda, Ana Carolina; Oliva, Ana L; Andres H Arias. Microplásticos
en corvina rubia (Micropogonia furnieri) del Estuario de Bahía Blanca,
Argentina. Argentina. San Luis. 2018. Libro. Artículo Breve.
Congreso. VII Congreso Argentino de la SETAC. SETAC Argentina.
[11] Fernandez Eleonora; Quintas, Pamela Y; Carla V. Spetter; Andres H
Arias; Garrido, Mariano; Jorge E. Marcovecchio. ESTUDIO
Preliminar Sobre El Rol De Diversos Parámetros Físicoquímicos En
La Dinámica De Los Compuestos ORGANOESTÁNNICOS. CASO
De Estudio: Puerto Rosales (Argentina. Argentina. Gral Roca. 2018.
Libro. Artículo Breve. Jornada. XVI Reunión Argentina de
Sedimentología, General Roca, Río Negro, 26-30 Nov 2018..
Asociación Argentina de Sedimentología.

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