Polytechnic University of the Littoral (ESPOL)

Faculty of Maritime Engineering, Biological,

Oceanic and Natural Resources (FIMCBOR)

Lead cycle in the ocean

Marine Pollution

Ph.D. Franklin Ormaza

Gema Camacho
Karen Galarza
Nicole Groenow
Karen Maruri
Génesis Mendoza
Nathaly Vargas

II term - 2018
Content
1. Introduction .............................................................................................................................. 2
2. Definition, chemical and physical properties on lead ............................................................. 3
3. Distribution in the open ocean ................................................................................................ 4
3.1 Vertical Distribution ............................................................................................................... 4
3.2 Horizontal Distribution ........................................................................................................... 5
3.3 Inputs and Outputs ................................................................................................................. 6
4. Budgets ..................................................................................................................................... 8
4.1 Lead flux in the ocean, rivers etc. .......................................................................................... 9
5. Processes in the open ocean .................................................................................................. 11
5.1 Internal processes ( biological o chemical) .......................................................................... 11
6. Impacts and risks in the marine enviroment and the humans ............................................. 12
7. Conclusions ............................................................................................................................. 13
8. Personal Opinion .................................................................................................................... 13
9. References .............................................................................................................................. 15
1. Introduction

Lead is a nonessential heavy metal already known in Egypt at least 4,000 years before
Christ. Its alloys with Sb and Sn go back to antiquity. The toxic effects of lead were described
more than 2000 years ago by Nicander, a Greek poet who wrote about a disease known as
plumbism, caused by acute lead poisoning. Later, lead poisoning was called lead poisoning
because alchemy considered lead to be the origin of other metals, and for that reason it was
dedicated to God Saturn, considered in mythology as the first of the gods. The Roman ruling
class suffered from lead poisoning due to the preservation of certain foods in copper containers
lined internally with lead plates. Lead has the ability to bioaccumulate so its concentration in
plants and animals is magnified along the food chain. The use and environmental pollution by
lead have increased enormously in the last 50 years as it has become evident in the sequential
ice sheets of Greenland. In 1780, at the beginning of the Industrial Revolution, 1 g of ice
contained 10 pg of lead. Two hundred years later, the concentration of lead in 1 g of ice was 20
times higher (200 pg), with greater increases after 1940. In the era of the Industrial Revolution,
lead poisoning became a problem of Occupational Medicine, because the largest number of
intoxicated workers were in certain industries that handled lead. Also, many painters, including
Goya, suffered poisoning from repeated contact with paints based on this metal. Nowadays,
however, food exposure to this metal is mainly of concern. (Rubio)

Lead poisoning occurs after exposure to this metal; This has many uses and sources such
as batteries for cars, additive in gasoline, cable coating, production of pipes, tanks, protection
of materials exposed to the weather, manufacture of ammunition, pigments for paints and
varnishes, glass making, ceramic enamelling, litharge, can welding, antiseptics (white Codex
water). Tetraethyl and tetramethyl lead are used as additives and antiknock of gasoline,
contributing to environmental pollution. "In Peru, according to Supreme Decree N ° 019-98-
MTC, there was a deadline until the end of 2004 to eliminate the lead content of gasoline"
(Infantas, 2005). Lead smelters, the manufacture and dismantling of batteries for cars and the
ceramics industry are the main source of work-related intoxication in our environment. "Before
1970 in the United States the paintings contained lead, which represented a serious problem at
the time, as children ingested the paint chips that fell off the walls and developed intoxication"
(Infantas, 2005). The difficulty for diagnosis is further increased when the source of exposure to
lead is unusual such as folk medicines, ceramics, ingestion of foreign bodies containing lead,
bone calcium supplements from animals, lead containers and retained bullets. injuries by
firearm among others.
2. Definition, chemical and physical properties on lead

Lead is a blue-gray chemical element with an atomic number of 82. Its symbol is Pb and it belongs
to the group of metals in block p and its usual state in nature is solid. Lead is located at position
82 of the periodic table. Lead belongs to the group of metallic elements known as p-block metals
that are located next to the metalloids or semimetals in the periodic table. This type of elements
tend to be soft and have low melting points, properties that can also be attributed to lead, since
it is part of this group of elements. (Elementos , s.f.)

Physical properties of lead (UNIPLOM, 2004)

Density (g/cm3) 11.34

Melting point (°C) 327.5
Boiling point (°C) 1750
Atomic number 82
Atomic weight 207.19
Oxidation +2 y +4
Specific heat (J·kg−1·K−1) 129.8
Thermal conductivity (W·m-1·K-1) 34.9
Resistivity to 20°C 20.6
Table 1 Physical properties of lead.
Source: www.uniplom.es/propiedades.htm

Chemical properties (Ensaostube, s.f.)

• When it is in contact with air, it oxidizes superficially, and this makes its shine disappear,
but it forms a basic carbon layer that protects it.
• Bad electrical conductor.
• Reacts with acids slowly.
• Resists well to hydrochloric and sulfuric acids but is attacked by nitric acid and sulfur
vapor.
• It has great resistance to corrosion.
• Slightly soluble in water.
• Form poisonous soluble compounds Pb(OH)2.
3. Distribution in the open ocean

3.1 Vertical Distribution

Figure 1 Vertical distribution of lead Source: (M. Boye B. D. Wake, 2012)

Pb is a marker of anthropogenic sources of dust and particles to surface waters and these
sources are higher in the South African margin than in the Southern Ocean. The highest dry
deposition flux of Pb is 0.14-0.22 nmol m-2. The waters in the South Atlantic region interact with
the platform waters and slopes, cyclones and filaments, and are expelled from the current of
the western border of the South Indian Ocean, the Agulhas Current, in its retroflection. (Pere
Masqué, 2012)

What is the decrease in Pb in the water column? Pb that is driven by the elimination of the
sinking particles, due to Pb concentrations in the Atlantic thermocline that decreased the
decrease in water levels on the surface of the ventilation waters. Pb has declined near the
Hawaiian Islands, but China's emissions have grown to a different story in the western Pacific.
The recent economic development and the phasing out of leaded gasoline in India, Indonesia,
China and several countries in South Asia have caused a high content in the north and center of
the Indian Ocean. The composition of the isotopes of the deep waters of the Antarctic in the
sector of India can be a major contribution of Pb in the natural crust, and above all of the
anthropogenic sources due to industrialization. (M. Boye B. D. Wake, 2012)
 Figure 2 Growth of the lead isotopes since 1880-2000 Source: (Ning Zhao, 2015)

Between the years 86-93, the first 30 years are produced in the subtropical turn, a favor of the
wind of both the emissions of EE. UU, as of some European countries. The atmosphere and
current of the North Atlantic are transported to the north, where it is carried by the wind
(Pump), the pump towards the thermocline and the cooling produce the creation of deep waters
in the winter. The news of the 1940s, at the end of the Second World War, increased the
prosperity of the USA. ("Two cars in each garage" that uses leaded gasoline) and European
prosperity. Lead levels on the surface of Bermuda reached more than 200 pmol kg-1 in the
1970s. This increase in Pb concentration has been followed and maximum Pb values of 210 pmol
/ kg have been obtained in the 1970s (of course, in the 1970s). The gradual elimination of leaded
gasoline. Since 2000, the amount of Pb has increased, due to intense industrial activity,
greenhouse gases, vehicular pollution, paints, gasoline, among other factors that have caused
serious changes in the ozone layer. (Ning Zhao, 2015)

3.2 Horizontal Distribution

Figure 3 Horizontal Distribution of lead Source: (Paulina Pinedo-Gonzalez, A. Joshua West, Antonio Tovar-
Sanchez, 2018)
The lowest concentrations were found in the southern hemisphere near New Zealand is 15 pm
and in the South Atlantic 10 pM. Pb concentrations in the northern hemisphere have always
been higher since the 20th century, due to the large number of industrialized countries that
surround the north. Despite the concentrations of dissolved Pb measured there are expressed
dozens of pico mol L-1, earlier when leaded gasoline was intensively used, the surface water
concentrations of the central oceanic turns had a higher magnitude (160 pM in the North
Atlantic Ocean).
The concentrations of dissolved Pb, the isotopes of Pb also varied geographically in the surface
waters of the world ocean. But the proportions of 206Pb / 207Pb and 208Pb / 206Pb changed
from 1,134 to 1,184 and from 2,071 to 2,111. The largest amounts are 206Pb / 207Pb were
located in the Northwest Atlantic Ocean, while the lowest proportions are in the Indian Ocean.
By contrast, the highest were 208Pb / 206Pb in the Indian Ocean a few miles from the Australian
coast and the lowest 208Pb / 206Pb in the North Atlantic and Northeast Pacific.

3.3 Inputs and Outputs

Inputs

Inputs of trace metals to the ocean that can stimulate phytoplankton production include
atmospheric deposition, freshwater inputs from rivers, upwelling along the coast and transport
of coastal sources to the open ocean within eddies. However, identification of essential trace
metal inputs is required large regions of the ocean demonstrating high nutrient low chlorophyll
(HNLC) conditions, where available nutrients such as nitrate and phosphate. Measurements of
dissolved Pb isotopes in the eastern subartic North Pacific HNLC identified distinct ratios
between North American river inputs and atmospheric deposition from Asia.

Since the 70s, due to the industrial revolution and the use of paints, steel, metallurgy leaded
gases were released, but by the atmospheric circulation through solidification there is a large
accumulation of lead in the ice layers of the poles and with the passage of time, that is, the
melting of the poles, has gradually been released into the atmosphere. Emissions in 1970
estimated that the majority occurred in the northern hemisphere, with urban and rural areas
accounting for the majority of emissions and deposits, including a large deposition in rural
localities downwind.

Lead from anthropogenic sources results in results greater than 10,000 μg / g. The soil in the
semester, the lead mines, the houses painted with lead paint, the traffic networks and the urban
areas, the excess of car traffic, is almost certain. The dust carried by the wind and the earth
include the lead that falls to the ground from the air, the withering and chipping of the paint of
the buildings and other structures. In the follow table shows the concentration.

Table 2 Lead amounts: anthropogenic and natural Source: (Astrid Sigel, 2015)
Ouputs

This mobilization of the lead occurs primarily through vehicular fuel combustion, non-ferrous
metal production and the burning of fossil fuels. Measurements made on material in the
atmosphere, as well as in rainwater soils, sediments and aquatic environments demonstrate
these anthropogenic activities result in significant enrichment in Pb relative to its average
concentration in the continental crust. Lead emissions to the atmosphere are largely from
anthropogenic sources and show higher levels near urban areas with the fluxes being temporally
variable, particulate Pb is diverse in size and chemical composition and is easily dispersed by
prevailing winds and subsequently delivered to the terrestrial and aquatic environment by wet
and dry deposition.

Mobilization of lead occurs through mining and smelting of ores, combustion of fossil fuels and
use, recycling and disposal of Pb containing products, but the economic depression in 1930’s
and 1940’s and a significant drop in Us production, but to the phase out of alkyl lead in gasoline
in 70 and 80 has been a increase in global production from -1000.000 t at the beginning of the
20 th century rapidly rising since 2000 to -5.500.000 t by 2013. In China there are a 2.300.000 t
and more minor contributions from Australia 633.000 t and USA 385.000 t.

Figure 4 Global Production vs years of lead Source: (ASLO, 2012)

Lead concentrations as high as 0.2 percent were found of the sediments; high heavy-metal
concentrations were associated with high concentrations in the river water. The most important
outputs of Pb alloys in industry are for Pb- acid batteries, ammunition/ballistics, oxides for glass
and ceramic hardening, casting metals, weights and shielding applications. Over the last 20
years, 80-90% of Pb consumed in USA was used to manufacture lead-acid batteries. This type of
battery enjoys widespread use in starting-lighting ignition batteries for automobiles and trucks
as well heavy industrial vehicles used in the mining, aviation and construction industries. Pb
containing are essential for medical and computing hardware as well as storage components of
load leveling systems associated with commercial power networks.
4. Budgets
There are several ways that an element such as lead reaches the ocean, among them we have
estuaries that deliver huge amounts of sediment, dragging minerals, soil particles and rocks with
them. We also find aerosols, which are nothing more than particles transported by air. Finally,
we consider the hydrothermal processes as part of the dynamics of input of different
elements to the ocean (Scott, 2012) .

Figure. 5 Cycle Global of Lead, where we observe the inputs and outputs. Source : (Olivero Verbel, 2015)

It should be noted that lead is not an essential element for the life of many organisms, resulting
in toxic change for living beings. Therefore, its concentration in the ocean is expected to be
minimal, presenting low concentration rates naturally. Of course , that like the rest of elements
and polluting metals this has been increasing because of the intervention of man.
The use of lead in industries has been decreasing as time passes, as it is highly toxic, causing
deaths around the world. Its danger is that can not be processed by the body and accumulates
inducing poisoning the body and generate irreparable damage.
As expected, its entry through estuaries is closely linked to lead dust dumps by industries , use
of lead paints, pipe wear among other contributions that we will generally call domestic waste,
in addition tomining upstream. But , none of these compares to the great impact that the ocean
had on the part of anthropogenic aerosols in 1923 , with the introduction of leaded
gasoline. However, if we take into account that its distribution in the ocean is not uniform, it is
a very reactive element and its residence time is approximately 80 years (pre-industrial deep-
water lead cycle). (Monterey Bay Aquarium Research Institute, 2017) , it is possible that the
amount of lead in the sea may decrease, and in fact it has been achieved. Being a dangerous
element for human health, the regulations for the use of leaded gasoline did not wait and in a
few years several countries were reducing their use. An example o f effort is surface water
carried North Atlantic Ocean, where it can be seen significantly declining concentrations of
lead(Environmental Research Doctoral Training Partnership, nd) . But on the other hand we have
some regions of the Indian Ocean, where the concentrations of lead have not decreased, but
are still increasing(Environmental Research Doctoral Training Partnership, nd) . The reasons for
this are due to several factors, contributions from industrial activities, and the transition that
some countries are still experiencing to finally leave leaded gasoline. As we observed in fig. 2
countries such as Algeria, Yemen and Iraq still use this FUELS and, being near this part of the
ocean, contributing to the increase lead.

4.1 Lead flux in the ocean, rivers etc.

Figure. 6 Leaded Petrol Phase-out: Global Status as at March 2017. Source: (UNEP, 2017)

Since there are many ways in which lead can be introduced into the marine environment, we
can find different ions of compounds with lead in the water as seen in fig. 3. Also, it is important
to mention that lead is an amphoteric and relatively reactive , so it usually forms many salts,
oxides and organometallic compounds (Lenntech, nd) . This means that the various marine
organisms can consume a portion of lead in one way or another without even noticing it. As
shown in fig. 1 the person who ingested this substance dies, dilutes, being a part assimilated by
another organism or depositing in the bottom where a thermal escape will return or it may be
mixed with groundwater. The same figure shows how lead in the form of salts is expelled
through a salt spray, where it can be moved to another part of the ocean or directly to the
ground.
Figure. 7 Distribution of lead in ecosystems. Source: (Olivero Verbel, 2015)

Although it is a very harmful element, its concentration in the ocean is much lower compared to
other metals. In addition, most of its agglutination is on the surface up to 1000m where it
decreases drastically.Its distribution in the vertical water column is vertical, when they reach the
depth of 1 km the dissolved lead settles in the bottom eliminating itself along with the rest of
the sediments.

Lead Depth P rofiles

Pacific Ocean33rd Atlantic Ocean34th

N, 155th W N, 66th W

Depth Pb (pmol Depth Pb (pmol /

(m) / kg) (m) kg)

0.2 65.7 0.2 160

75 58.9 35 150

200 63.3 100 160

400 67.6 150 160

600 43.0 400 170

800 27.5 600 150

1000 21.7 750 130

2000 9.7 1000 77

2500 6.3 1470 77

3000 8.2 2070 43

3500 4.8 2440 27

4000 5.3 2980 26

Table 3. Distribution of lead in the depth. Comparison between Pacific Ocean and
Atlantic Ocean . Source : (Monterey Bay Aquarium Research Institute, 2017)
5. Processes in the open ocean

5.1 Internal processes ( biological o chemical)

Lead is a metal that has been introduced into the processes of the ocean due to the action of
man mainly by the use of fuel containing lead between the 1920s and 1970s. The process of
dissolution of this metal has not been studied much yet, but it is known to cause toxicological
damage when organisms assimilate it. The cycle of this heavy metal begins when the
atmosphere absorbs the waste of the industry and distributes it all over the world. Much of this
metal is absorbed by the ocean due to currents and is concentrated in water masses, altering its
chemical composition and causing effects on the food chain.

Lead, like all metals, is a substance that accumulates in the bottom but is incorporated in the
species that filter in the water, such as mollusks, cockles and clams. From there it is transported
when the species feed on them. This substance accumulates in organisms quickly and
progressively but it takes a long period of time to be eliminated by the body.

When the lead comes into contact with water and humid air, its reactivity is high and a layer of
lead oxide (PbO) is formed; in the presence of oxygen and water, the metallic lead is converted
to chromium hydroxide (Pb (OH) 2):

2Pb (s) + O2 (g) + 2H2O (l) -> 2 Pb (OH) 2 (s)

This reaction occurs in the ocean and from there they are absorbed by the species and have
effects such as exposure to lead causes serious alterations in the organism: binds and inactivates
the -SH group of proteins, inhibits the biosynthesis of the heme group (limiting origination in the
body), displaces Calcium accumulating in the bones, which limits the absorption of Calcium for
bone and blood development, muscle contraction and nerve function (it is neurotoxic).

Figure 8 Biogeochemical cycle of lead a: inhalation; b: precipitation/ deposition; c: evapotranspiration; d:

degradation; e: absorption / adsorption f: volcanic activity; g: mechanical wear (erosion, weathering) i:
evaporation; j: aerosol k: solution; l: mineralization; m: leaching. Source: Research Gate
6. Impacts and risks in the marine enviroment and the humans

In humans, the effects of lead were first documented in children approximately a century ago,
but how does lead get into the body? Lead can get into the body by ingestion, by inhalation or
by skin absorption, it can be trough water or other substances or objects that contain this metal.
Nowadays, the Environmental Protection Agency limits the amount of lead in water to 15
micrograms per liter, though some toxicologists think that limit should be lowered to 10
micrograms per liter. One of the terrible impacts of lead is that it sticks to red blood cells and
then it moves into soft tissues such as liver or lungs. Another scenario can be that lead is
absorbed into the bones or it affects the brain, like Schneider says “It can really change the
programming of the brain, which will have considerable effects on subsequent behavioral and
brain function. As we learn more about lead and its effects on the brain, even down to these
molecular levels, if anything it’s even more dangerous than we thought.”. Also, other health
problems caused by lead can be:

➢ Disruption of the biosynthesis of hemoglobin and anemia

➢ A rise in blood pressure
➢ Miscarriages and subtle abortions
➢ Disruption of nervous systems
➢ Declined fertility of men through sperm damage
➢ Diminished learning abilities of children
➢ Behavioral disruptions of children, such as aggression, impulsive behavior and
hyperactivity

On the other hand, fetus can be affected too by lead since it can enter through the mother’s
placenta damaging the nervous system and the brain of an unborn child.

Moreover, humans are not the only ones affected by lead but also the environment and the
marine ecosystem. Lead accumulates in both, water organisms and the organisms that are in
soil, these will be affected by lead poisoning. Shellfish health affections by this metal can take
place with the presence of only small concentrations. In phytoplankton, lead interrupts body
functions affecting not only other organisms that eat them but also the source of oxygen
phytoplankton produce, letting us know that lead pollution can influence global balances by
having an impact in the entire food chain.

In fishes, lead toxicity symptoms include spinal deformity and blackening of the caudal region.
In dolphins, lead is transferred from mothers to offspring during fetal development and lactation
causing death. The authors suggested that lead was removed from the mother via the milk and
as the result of parturition. On the other hand, soil is also contaminated by lead because this
metal is a dangerous chemical that can accumulates damaging the composition of the oceans
floor. It is also important to emphasize that the lead present in the water columns depends on
factors like water chemistry, solubility, salinity and organic matter content.
7. Conclusions

• Lead is a major constituent of the lead-acid battery used extensively in car batteries. It
is used as a coloring element in ceramic glazes, as projectiles, in some candles to threat the wick.
It is the traditional base metal for organ pipes, and it is used as electrodes in the process of
electrolysis. One if its major uses is in the glass of computer and television screens, where it
shields the viewer from radiation. Other uses are in sheeting, cables, solders, lead crystal
glassware, ammunitions, bearings and as weight in sport equipment. (LENNTECH )

• Lead occurs naturally in the environment, yet, most lead concentrations that are found
in the environment are a result of human activities. Due to the application of lead in gasoline an
unnatural lead-cycle has consisted. This lead-cycle caused by human production is much more
extended than the natural lead-cycle. It has caused lead pollution to be a worldwide issue.
(Science Learning Hub )

• When the lead salts enter the environment through the exhausts of cars, the larger
particles will drop to the ground immediately and pollute soils or surface waters and the smaller
particles will travel long distances through air and remain in the atmosphere. (gdrc)

• Lead accumulates in the bodies of water organisms and these will experience health
effects from lead poisoning, for example, health effects on shellfish because the body functions
of phytoplankton can be disturbed when lead interferes. (NCYT)

• In the last 50 years, corals have been used to trace the history of anthropogenic lead.
(Pizarro, s.f.)

8. Personal Opinion

Lead is one of the metals that some decades ago began to be studied because it has a lot of
consequences in the body and produces many damages and alterations in species such as
mutations or genetic alterations of sex. It is important to remember that planet earth is a
dynamic system where everything that takes place in an area has consequences throughout the
world, in the years between 1920 and 1970 there was no awareness of the risk of this metal and
that is why they were deposited in great amount of toxic substances that contained it and that
continue to impact in marine environments. There are recent studies that indicate that the
melting of the poles is due to the excess of lead in the ocean, but many studies are missing to
prove that this is the case. We must be aware of our actions because if they are not controlled,
they could soon have effects that destroy the possibility of life on earth. (Groenow Nicole)

There are many studies that reveal that lead concentrations are high in the Indian Ocean, the
North Atlantic and the North Pacific. We know that lead is a particularly dangerous chemical, as
it can accumulate in individual organisms, but also in entire food chains, yet, we do nothing to
lessen the use of lead. Lead is a heavy metal which means that is compounds are toxic, that is
why today there are many diseases, contaminated waters and soils. (Maruri Karen)

Data shows that in 2015, half a million people around the world died from exposure to lead due
to the lack of control in the regulation of the use of this metal. The first step as individuals is to
let more people that unknows be aware of the terrible effects of lead to human’s health and the
damage this causes to the environment and marine ecosystem, and not only that but encourage
for the approval of laws that prohibits the inadequate and excessive use of lead. And to the last
but not least, everyone should start the prevention at home. (Camacho Gema)

The effort of the nations of the world to reduce the concentrations of lead has become very
evident, since the concentrations of this toxic metal have decreased by almost 50% (Bridgestock,
et al., 2016) . This is mainly due to the reduction and almost elimination of leaded gasoline. It is
true that mainly its regulation is because the lead is dangerous for humans. However, it is an
achievement that, although it took around 50 years to happen, should not be taken lightly, since
it shows that if the nations of the world come together under one same goal, great works can
be achieved. Returning to the issue of its distribution and cycle in the marine environment, it is
important to clarify that, due to the restriction of this fuel, the lead in the surface has decreased
its concentration, because the quantity brought by aerosols also decreased. Est
deposits and element will become part of the cycle of renewal of land in the best and at worst
will go to groundwater. Therefore, it is necessary that attention be paid to this matter because
these waters are our future reserves of fresh water. (Vargas Nathaly)

Lead, not only has harmful effects on the environment but also on health, for example the excess
of lead in blood also known as lead poisoning, it is more serious at the neurological level causing
problems irreversible, in children affecting brain development, the average lead time in blood is
30 days; a part of this enters in the body is absorbed and transported to different organs, body
tissues human affecting all systems. In Ecuador there are works to evaluate the pollution
produced by the lead executed in the environment, both in soil in water superficial, marine
organisms such as the mangrove oyster, in addition to the naval personnel who use fuel with
lead. That is why it is important to establish regulations to regulate environmental damage and
prevent catastrophic illnesses. (Galarza Karen)
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