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c.

Chlorinated Dibenzofurans
Another group of halogenated hydrocarbons that has received
considerable attention in recent years because of the multiple
impacts of the contaminants on aquatic organisms includes the
chlorinated dibenzo-p-dioxins (CDDs) and chlorinated
dibenzofurans (CXDFs).
These aromatic heterocyclic compounds appear to be highly toxic
to marine organisms, and they can induce serious sublethal effects.
Occurring as trace contaminants in organic chemicals, such as
chlorinated phenols, PCBS, and phenoxy herbicides.
CDDs and CDfs enter estuarine and marine environments via
wastewater discharges, groundwater inflow, sewer overflows,
storms drains, and atmospheric deposition.
CDDS and CDFs are widely distributed in seawater and sediments
at low parts-per-trillion concentrations.
Being environmentally persistent and highly lipophilic compounds,
CCDs and CDFs tend to bioaccumulate in marine organisms by
food chain transfer rather than by direct uptake from seawater,
suspended matter, or bottom sediments.

d. Effects on Biotic Communities

Halogenated hydrocarbons pose a potentially serious threat to the


structure of estuarine and marine communities because some
species, particularly those occupying upper tropic levels,
accumulate the contaminants to very high levels and, hence, are
susceptible to chronic chemical exposure.
The high mortalities of harbor seals, together with diminished
hatching success of marine birds exposed to DDT and PCBS,
provide examples.
Field investigations will continue to be extremely difficult to
conduct because a single sample collected at an impacted site may
contain as many as 100-150 different halogenated hydrocarbon
compounds.

2. Heavy Metals

a. Composition and Sources


One of the less desirable by-products of an industrialized society is
the increase of heavy metal accumulation in marine environments.
Heavy metals may be grouped into two categories:
1. Transitional metals: Transitional metals (e.g. copper, cobalt, iron,
and manganese) include those elements essential for metabolic
function of organisms at low concentrations but may be toxic at
high concentrations.
2. Metalloids: (e.g., arsenic, cadmium, lead, mercury, selenium, and
tin) are generally not required for metabolic activity but may be
toxic at low concentrations.

Estuarine and oceanic waters receive heavy metals from both


natural and anthropogenic sources.
Natural processes (e.g., weathering and erosion of rocks,
leaching of soils, eruption of volcanoes, and emissions of
deep-sea hydrothermal vents).
Anthropogenic inputs are usually much greater in coastal
waters near urban or industrialized centers.

b. Metal Toxicity
Heavy metals are toxic to marine organisms. The approximate
order of increasing toxicity of heavy metals, according to Abel,79
is a s follows: Co, Al, Cr, Pb, Ni, Zn, Cu, Cd, and Hg.
However, the toxicity of a given metal varies in estuarine and
marine organisms for several reasons :
(1) The capacity of the organisms to take up, store, remove, or
detoxify heavy metals differs considerably.
(2) Many intrinsic and extrinsic factors influence heavy metal uptake:
intra and inter-specifically variable intrinsic factors, such as
surface impermeability, nutritional state, stage of molt cycle, and
throughout of water by osmotic flux.
(3) Extrinsic physico-chemical factors, such as dissolved metal
concentration, temperature, salinity, presence or absence of
chelating agents, and presence or absence of other metals.
Once assimilated by marine organisms, heavy metals may be
sequestered by metallothioneins and lysosomes, thus facilitating
detoxification processes. Metal binding activity of metallothioneins
and lysosomes is also variable in marine organisms.

The toxicity of trace metals has been coupled to the free metal
ionic activity regardless of the total metal concentrations. In
marine environments, heavy metals occur in dissolved form (as
free ions, complexes ions, etc.) or in the solid state (as colloids,
adsorbed onto particle surfaces, in mineral matrices, etc.) They
may be present as inorganic and organic species.
At toxic levels, heavy metals act as enzyme inhibitors in marine
organisms. They also adverse affect cell membranes.
Organometallic species often damage reproductive and central
nervous systems.
Other disruptions include changes in physiology and development.
Feeding behavior, digestive efficiency, and respiratory metabolism
commonly are adversely affected.

a. Metal Concentration
i. Copper
The levels of copper in estuarine waters (-0.2 to > 100 g) are usually
much greater than those in oceanic waters (~0.1 g/1) because
dissolved copper sorbs to particulate matter, the concentrations in
bottom sediments can be a substantial. A positive correlation exists
between the concentrations of copper in sediments and those observed
in many benthic species.

ii. Cadmium
The concentrations of cadmium in coastal waters removed from
industrialized centers range from 1-100 ng/1. Where inputs are
elevated because of industrial or municipal waster disposal.
Cadium accumulates in bottom sediments at, cadmium
concentrations generally range from 0.1-10.0 g/g, dry wt.
Mussels (Mytilus spp.) used as sentinel organisms in coastal
regions have accumulated cadmium to mean levels of 1-5 g/g
dry wt.

iii. Lead
The concentrations of lead in the open ocean range from 0.001-
0.014 g/1. Lead levels in estuaries and coastal marine waters
exceed those in the open ocean by a factor of 10 or more.
Organ lead compounds are generally more toxic to marine
organisms than inorganic forms. The amount of lead in marine
mammals (i.e., dolphins, porpoises, seals, and whales) from
waters around the British Isles is 0.05 7.0 g/g wet wt.2

Mercury

Mercury in marine environments include elemental mercury,


divalent mercury ions (Hg2+), and methyl mercury ((CH3)2Hg).
Mercury readily sorbs to particulate matter and tends to
accumulate in bottom sediments. Most of the mercury
accumulating in shellfish (40-90%) and finish (>90%) is methyl
mercury. The levels of mercury in marine mammals (i.e.,
dolphins, porpoises, and seals) generally are between 03 and
430.0 g/wet wt.
iv. Tin
Inorganic tin concentrations in open ocean waters vary from
0.003-0.008 g/1. Localized elevated levels of dissolved tin,
approaching 50 g/1, have been documented in coastal waters
receiving industrial discharges. Marine invertebrates can
accumulate significant levels of tin

Effects on Biotic Communities.


Dissolved copper concentration of 1-10 g/1 have been shown in
the laboratory to increase mortality of young bay scallops,
species diversity of benthic faunal communities in Norwegian
fjords showed a strong negative correlation with copper
concentrations in bottom sediments.
Even at extremely low levels, cadmium may adversely affect
benthic organisms.
A negative correlation between bacterial biomass and cadmium
concentrations in the northern Tyrrhenian Sea, with high
cadmium concentrations possibly arresting bacterial
development.
Plankton populations are also very sensitive to cadmium.
The toxicity of inorganic lead to marine organisms is less than
that of may other heavy metals. Under experimental conditions,
marine organisms display adverse effects of inorganic lead only
when concentrations are about 100 times greater than those in
coastal waters.
The presence of organo-tin compounds in marine waters has
assumed increasing significance in recent years in regard to
impacts on biotic communities.
When exposed to tributyltin (TBT) concentrations as low as 0.01
g/1, marine invertebrates often exhibit changes in growth and
reproduction. Oyster shell abnormalities, reduced growth rates
in mussels, imposex in stenoglossan gastropods, failure of
recruitment in clams, and breakdown of sexual differentiation
and failure of settlement in oysters have all been linked to TBT
exposure (Table 23).
Organotins can be magnified to relatively high proportions in
invertebrates (commonly >60%).
Food chain magnification of TBT does not appear to occur in
higher organisms (i.e., crustaceans, fish, and mammals),
however, because they possess the necessary enzymes to break
down the contaminant relatively rapidly.
TBT is extremely toxic to many marine organisms; it is not very
stable and degrades to less toxic compounds in a few weeks in
marine, environments.

7. Radioactivity
a. Sources
i. Natural Sources
Radionuclides in estuarine and marine environments derive from
both natural and anthropogenic sources (Tables 24-26).
Natural background radiation is attributable to cosmogenic and
primordial radionuclies.
Cosmogenic radionuclides originate from the interaction of
primary cosmic rays with matter in the atmosphere and on the
surface of the earth.
The collision of high energy particles (cosmic radiation) with
nitrogen, oxygen, argon, and other atoms in the upper atmosphere
produces secondary particles, primarily neutrons and protons.
Secondary cosmic radiation accounts for nearly all cosmic rays
impinging on the sea surface.
Primordial radio nuclides are those that were generated at the time
of formation of the earth.

ii. Anthropogenic Sources


Since 1944, artificial radioactivity has entered estuarine and marine
environments from several major anthropogenic sources, namely
nuclear weapons testing. The relative importance of these
anthropogenic sources of radionuclide has changed over the past 50
years.
Between 1945 and 1980, most artificial radionuclide entering the
sea originated from nuclear weapons testing.
More than 1200 nuclear weapons tests were conducted throughout
the world during these 35 years, with the major bomb testing
programs conducted between 1954 and 1962.
After the Partial Nuclear Test Ban Treaty of 1963, underground
nuclear weapons testing became most important, and atmospheric
weapons fallout to the sea diminished substantially.
Atmospheric fallout of radionuclides from nuclear weapons testing
has been about four times greater in the northern hemisphere than
in the southern hemisphere.
A number of fission products of nuclear detonations in the
atmosphere are biologically significant in the sea, notably
carbon (14C), cesium (137Cs), strontium(89Sr, 90Sr), and iodine (131I)
isotopes.
Anthropogenic sources of radioactive materials in the sea have
become important, particularly those associated with the
nuclear fuel cycle. Radioactive waste is produced at various
stages of the nuclear fuel cycle (i.e., mining, milling, conversion,
isotopic enrichment, fuel element fabrication, reactor operation,
and fuel reprocessing) (Figure 14).
Major accidents at nuclear power plants, such as at the Three
Mile Island in Pennsylvania and Chernobyl in the Ukraine,
release considerable activity that may be detected in seawater
samples. In the case of Chernobyl, radio sink levels in muscle
of fish fro the southern Baltic Sea increased three- to four-fold,
and Cs,
134 Cs, and
137 106 Ru in fish in the Danube River increased
five-fold.
The disposal of radioactive materials in the sea has been
restricted to low level wastes released via discharges from land-
based sources or direct dumping of packaged wastes.