1.3 Common Heavy Metals in the Marine Environment
7
waterfront structures (Brown and Eaton 2001), dumping of sewage sludge (Pastorok
and Bilyard 1985; Guzmán and Jiménez 1992), using additives in drinking water to
control algal growth (Rieuwerts 2015), agriculture (the use of copper-based fungicides and as impurities in many pesticides, fungicides and algaecides), ship groundings resulting in localized contamination (Haynes et al. 2002; Negri et al. 2002;
Smith et al. 2003) and intensive animal farming.
Cu is also a major component of antifouling paints (Claisse and Alzieu 1993;
Howe et al. 2014), present in industrial, urban and agricultural discharges (Mance
1987; Reichelt-Brushett and Harrison 1999) and is a component of some fungicides
and herbicides that are used on coastal agricultural crops (Cremlyn 1979).
Smith et al. (2003) mentioned that tributyltin (TBT) had been applied on large
vessels together with Cu and Zn as an antifouling biocide. The biocides are specifically designed and chosen to prevent settlement and growth of algae and invertebrates
(Jones 2007) on marine vessels. TBT rapidly kills organisms such as mussels and
barnacles, which attach themselves on ship hulls and hard surfaces. TBT was the
most widely used active component in antifouling paints; however, a global ban was
sanctioned in 2008 on the application of TBT paints (Tornero and Hanke 2016).
TBT caused negative environmental impacts signs of imposex in marine invertebrate
species and the deformation of oyster shells. Hence, biocides such as copper (I) salts,
mainly in the form of copper oxide (Cu 2 O) and copper thiocyanate (CuCHNS), have
been the main alternatives to TBT in many antifouling coatings (Tornero and Hanke
2016).
It is well documented that Cu is an essential element required by all living organisms; however, at higher concentrations it may accumulate and cause toxicity in
marine organisms (Bielmyer et al. 2005, 2010, 2012; Kim et al. 2008; Main et al.
2010; Bielmyer and Grosell 2011; Patel and Bielmyer-Fraser 2015; Siddiqui and
Bielmyer-Fraser 2015; Siddiqui et al. 2015; Bielmyer-Fraser et al. 2018). The speciation and bioavailability of Cu in seawater is greatly reliant on seawater chemistry
(Millero et al. 2009; Zeng et al. 2015).
Cu mostly exerts toxicity by altering enzyme function, causing oxidative stress,
disrupting ionoregulation, and/or disrupting acid/base balance in aquatic organisms
(Crespo and Karnaky 1983; McGeer et al. 2000; Bielmyer et al. 2005; Grosell
2011; Patel and Bielmyer-Fraser 2015; Siddiqui and Bielmyer-Fraser 2015; Siddiqui
et al. 2015; Bielmyer-Fraser et al. 2018). Cu causes endocrine disruption in aquatic
organisms (Rieuwerts 2015).
Solomon (2009) reported that Cu is one of the most toxic metals to aquatic organisms and ecosystems and occurs as the cupric ion (Cu
+2 ). The effects of copper on
aquatic organisms can be directly or indirectly lethal; for example: fish gills become
ragged and lose their ability to regulate transport of salts such as sodium chloride
and potassium chloride into and out of fish; and Cu adversely affects olfaction (sense
of smell) in fish (Solomon 2009). Cu is bioaccumulative in some organisms such as
plankton, oyster and squid by factors of up to 10
7 but it does not magnify in the food
chain (Rieuwerts 2015).
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