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Chapter 3
*
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.
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
MANAGEMENT
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.
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.
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
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
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
*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
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
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
TOXICITY
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.
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).
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.
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.
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
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.
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.
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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BIOGRAPHICAL SKETCH
Education:
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
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