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Applied Marine Biology - Aquaculture, Pollution and Conservation

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Heavy Metals in the Marine Environment

Lecture 1 by Dr Rick Leah

(A copy of the Overheads (as handed out in the Lecture is available here as a Word File )
(Suggested Books for this course )

"1. Basis for action
114. Heavy metals are natural constituents of the Earth's crust. Human activities have drastically
altered the biochemical and geochemical cycles and balance of some heavy metals. Heavy metals
are stable and persistent environmental contaminants since they cannot be degraded or destroyed.
Therefore, they tend to accumulate in the soils and sediments. Excessive levels of metals in the
marine environment can affect marine biota and pose risk to human consumers of seafood.
115. Metals and their compounds, both inorganic and organic, are released to the environment as
a result of a variety of human activities. A wide range of metals and metallic compounds found in
the marine environment pose risks to human health through the consumption of seafood where
contaminant content and exposure are significant. Many metals are essential to life and only
become toxic when exposures to biota become excessive (i.e., exceed some threshold for the
introduction of adverse effects). While certain non-essential metals do not have explicit exposure
thresholds for the introduction of effects, the nature of biological responses to metal exposure are
a direct consequence of exposure and are defined through dose-effect relationships. This differs
from the dose-response relationship associated with many synthetic organic contaminants and
radionuclides where risk of adverse effects is assumed to be proportional to exposure.
Accordingly, it is desirable to minimize such exposures. In contrast, the predominant challenge in
the case of heavy metals is one of limiting exposure to levels that do not cause adverse effects.
116. The main anthropogenic sources of heavy metals are various industrial point sources,
including present and former mining activities, foundries and smelters, and diffuse sources such as
piping, constituents of products, combustion by-products, traffic, etc. Relatively volatile heavy
metals and those that become attached to air-borne particles can be widely dispersed on very large
scales. Heavy metals conveyed in aqueous and sedimentary transport (e.g., river run-off) enter
the normal coastal biogeochemical cycle and are largely retained within near-shore and shelf
regions.

2. Objective/proposed target
117. The objective/proposed target is to reduce and/or eliminate anthropogenic emissions and
discharges in order to prevent, reduce and eliminate pollution caused by heavy metals."

From the UNEP document:
GLOBAL PROGRAMME OF ACTION FOR THE PROTECTION OF THE MARINE ENVIRONMENT FROM LAND-BASED ACTIVITIES Nov 1995

 

The metals of Particular interest in the context of this course (because of their toxicity) are :

Metals occur in varying amounts in sea water and since the sea is the final repository of soluble elements from the terrestrial part of the planet all are present. Some (so-called Heavy Metals), such as iron, copper, cobalt and zinc are essential in small quantities for the healthy growth of marine organisms (although they may be toxic when present to excess). Others, such as mercury, lead and cadmium have no known biological role. All of these metals are toxic if present in excess but the most important marine contaminants are generally considered to be those non-essential heavy metals.

Mercury

(Our own website on Mercury is now available)

Of the heavy metals, most attention is currently paid to Mercury because it still poses the greatest threat to human health from pollution of the marine environment. There are continuing efforts to tighten environmental restrictions on this element as new research reveals that it may be causing neurological damage to unborn and young children.

In marine sediments bacteria may convert the less toxic, inorganic form of the metal to the more toxic, organic form of methyl mercury. This chemical form is relatively mobile in the environment and tends to accumulate in fish. Consumption of marine (or other) food containing methyl mercury over an extended period may lead to the onset of Minimata disease. This disease, first observed in Minimata Bay in Japan where the local fish-eating community received large doses of mercury derived from a local chemical factory manufacturing acetaldehyde and vinyl chloride, has neurological symptoms which include, mental disturbance, ataxia and impairment of gait, speech and hearing. In the original incident a considerable number of fatalities (43) were caused with many more people (>700) being irreversibly affected. Mercury is an important industrial material used, for example, in the chlor-alkali industry and in the manufacture of small batteries. 

Mercury is a natural contaminant of the marine system and since methyl mercury moves up the food chain easily (in some circumstances actually biomagnifying) some large predatory fish such as tuna and swordfish have naturally high levels which may approach or even exceed acceptable limits for human consumption in large, older specimens. There are normally no apparent adverse health effects in the fish themselves, the risk is to the next level of consumer in this case humans. (However, wildlife such as birds can be adversely affected directly )

Mercury in tuna has recently been back in the news because of the risk to pregnant women and the unborn foetus (Guardian Article on the risk to pregnant women) This recent, elevated interest in mercury was partly generated by the very large number of US States that have had to  issue consumption advisories on wild fish populations (see this map which shows the scale of the problem).

Lead in the Mersey Estuary

Lead has been widely used for millennia and lead poisoning from non-marine sources is a well known phenomenon. Although use of lead, particularly as an additive to automobile fuel , has led to measurably higher concentrations in remote ocean waters there is no suggestion that harmful effects are occurring from this dispersal. There have been one or two incidents where ships carrying alkyl lead compounds (the chemical form used as fuel additive) have lost some of their cargoes but these have not resulted in any obvious harm and the only known instance of marine lead pollution occurred in 1979/80 in the River Mersey estuary  where alkyl lead caused many deaths amongst local seabird populations. This problem was caused  by lead tetraethyl being discharged at low concentrations from the manufacturing plant via the Manchester Ship Canal into the estuary at Ellesmere Port. This organo-lead compound was taken up by invertebrates (bioaccumulation) and passed up the food chain to wading birds causing many deaths at various stages of the tide. (This was probably a case of biomagnification although the data to suppot this are sparse)

For humans the amount of dietary lead received from most marine food is trivial compared with other sources such as drinking water.

Cadmium

Cadmium is very toxic and mobile in ecosystems. Cadmium, like mercury, is an industrially important metal which is used directly in electroplating and is also found in processes associated with zinc and phosphorus. Although cadmium has no known biological role it is taken up by marine phytoplankton; apparently by the same mechanism employed for the uptake of the essential nutrient element phosphorus. It has been demonstrated to stimulate phytoplankton growth and photosynthesis up to surprisingly high concentrations. Even in quite heavily contaminated marine systems cadmium is very unlikely to cause acute toxic effects to marine animals but there have been at least two instances where cadmium pollution has apparently been responsible for adverse effects to humans. The best known example of this was the outbreak of itai-itai disease in Japan which affected a village on the Jintsu river in Japan. The use of irrigation water, contaminated with cadmium from a zinc processing plant, in paddy fields was originally identified as the cause of the problem but other factors such as malnutrition and vitamin deficiency have also been cited as major contributory parameters. Itai-itai disease is characterised by brittle bones and considerable pain (the name means 'ouch-ouch') and the symptoms can be alleviated by the administration of large doses of vitamin D. A marine example of cadmium poisoning was caused by the consumption of contaminated Tasmanian oysters which led to nausea and vomiting in the victims.

Recently, Cadmium has become of concern in the Baltic Sea where changing oxygen conditions in deep water caused by eutrophication may be mobilising the metal. Levels in fish liver in the Baltic are increasing as a consequence.

Cadmium is one metal which has never been a significant pollutant of the Mersey Estuary but it was a problem from the fertiliser factory run by Allbright and Wilson at Whitehaven. There, as a consequence of processing phosphate rock, the highest concentrations of cadmium in blue mussels around the UK coastline were measured by Greenpeace. This eventually resulted in the first successful private prosecution for marine pollution by Greenpeace and the regulation of the discharges by Environment Agency. As a consequence, the plant was closed and most phosphate rock now gets processed in the developing world where environmental standards are not necessarily as tight.

Tin

Tin (in the form of the organo-tin compound tri-butyl tin known as TBT) has recently been recognised to be quite a serious marine pollutant. The use of organo-tin compounds in anti-fouling paints on boats has resulted in comparatively high concentrations of these chemicals in some enclosed waters (harbours, marinas etc.). Although very effective as anti-fouling agents, organo-tins also affect non-target organisms causing shell deformations in oysters and imposex in the common dogwhelk (Nucella lapillus). The use of organo-tins in cages used for farming fish has also led to concern. Many countries have now banned or severely restricted the use of organo-tin anti-foulants though the chemicals are still used in some other applications such as wood preservation.


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