Copper (Cu)

  1. Ocean and Aquatic Ecosystems:

    a. Toxicity to Marine Organisms: Copper is highly toxic to marine organisms, including fish, shellfish, and various marine invertebrates. It can impair their respiratory systems, damage gills, and disrupt ion regulation, leading to reduced growth, reproductive impairment, and even mortality.

    b. Bioaccumulation and Biomagnification: Copper has the potential to accumulate in the tissues of aquatic organisms. Through the process of biomagnification, copper concentrations can increase along the food chain, especially in predatory organisms at higher trophic levels. This bioaccumulation and biomagnification can result in high copper concentrations in top predators, making them more vulnerable to the toxic effects of copper.

    c. Disruption of Ecosystem Balance: Copper pollution can disrupt the balance of marine ecosystems by reducing species diversity and altering community structure. Sensitive species may decline or disappear, while copper-tolerant species may dominate, leading to imbalances in predator-prey relationships and ecosystem functioning.

  2. Rivers and Freshwater Ecosystems:

    a. Toxicity to Aquatic Organisms: Similar to marine ecosystems, copper pollution in rivers and freshwater bodies can be toxic to aquatic organisms, including fish, amphibians, and invertebrates. Copper interferes with their respiratory systems, damages gills, impairs reproduction and can cause overall population declines.

    b. Impact on Aquatic Plants: Copper pollution can hinder the growth and development of aquatic plants. It can inhibit photosynthesis, disrupt nutrient uptake, and lead to reduced biomass and impaired ecological functions, such as oxygen production and habitat provision.

    c. Disruption of Nutrient Cycling: Copper pollution can disrupt nutrient cycling in freshwater ecosystems. It can negatively impact the activity of microbial communities responsible for nutrient transformation and cycling, leading to imbalances in nutrient availability and utilisation.

  3. Soil Ecosystems:

    a. Soil Microbial Communities: Copper pollution can have toxic effects on soil microbial communities, including bacteria, fungi, and archaea. It can reduce microbial diversity, inhibit enzyme activity involved in nutrient cycling, and disrupt important soil processes such as organic matter decomposition and nutrient mineralization.

    b. Plant Growth and Nutrient Uptake: High copper levels in soil can directly impact plant health and growth. Copper toxicity can cause root damage, reduce nutrient uptake, and lead to nutrient imbalances, resulting in decreased plant productivity and overall vegetation diversity.

    c. Soil Fertility and Structure: Copper pollution can negatively affect soil fertility by disrupting nutrient availability and microbial activity. It can inhibit the decomposition of organic matter, leading to reduced nutrient cycling and the deterioration of soil structure, impacting water infiltration and nutrient retention.

  1. Industrial Discharges: Industrial processes, such as mining, smelting, and metal refining, can release copper-containing wastewater or effluents into nearby water bodies.

  2. Agricultural Runoff: The use of copper-based pesticides, fungicides, and fertilizers in agriculture can lead to copper runoff into soil and water.

  3. Domestic Wastewater: Copper from household plumbing, wastewater treatment plants, and septic systems can be discharged into rivers and oceans.

  4. Stormwater Runoff: Copper from urban areas, including roads, rooftops, and industrial sites, can be washed off during rainfall and carried into water bodies.

  5. Landfills and Waste Disposal: Improper disposal of copper-containing waste materials, including electronics, batteries, and other products, can result in leaching of copper into the soil and groundwater.

  6. Atmospheric Deposition: Copper particles released into the air through industrial emissions or combustion processes can deposit onto land and water surfaces through rainfall or dry deposition.

  7. Copper Mining and Extraction: Copper mining operations can release copper-containing dust, tailings, and wastewater into the surrounding environment.

  8. Metal Plating and Finishing: Processes like electroplating and metal finishing can involve the use of copper-containing chemicals, leading to potential copper releases.

  9. Paints and Pigments: Some paints, particularly those used in marine applications or outdoor structures, may contain copper-based compounds that can leach into the environment.

  10. Copper Alloy Production: The manufacturing of copper alloys, such as brass and bronze, can result in copper pollution through emissions, wastewater, and solid waste.

  11. Copper Wire and Cable Production: Copper wire and cable manufacturing processes can generate copper waste and emissions if not properly controlled.

  12. Printed Circuit Board Manufacturing: Copper is widely used in electronic circuit boards, and improper disposal of waste from the manufacturing process can lead to copper pollution.

  13. Wood Preservation: Copper-based wood preservatives, such as copper chromate or copper arsenate, can leach into the soil and water from treated wood products.

  14. Copper Roofing and Building Materials: Weathering and runoff from copper roofing and building materials can contribute to copper pollution in nearby soils and water bodies.

  15. Copper Plumbing and Pipelines: Aging or corroded copper pipes can release copper particles into drinking water and wastewater systems.

  16. Copper Processing and Recycling Facilities: Facilities involved in processing or recycling copper can potentially release copper particles and wastewater during their operations.

  17. Shipbuilding and Marine Industry: Antifouling paints used on ship hulls often contain copper compounds to prevent the growth of marine organisms, leading to copper leaching into the water.

  18. Copper Alloy Foundries: Foundries involved in the production of copper alloys may release copper-containing dust, emissions, and wastewater.

  19. Electrical and Electronic Equipment Manufacturing: The production of electrical and electronic devices, such as computers and mobile phones, can result in copper pollution if not properly managed.

  20. Art and Craft Activities: Copper-based materials and products used in artistic or craft activities, such as jewellery making or sculpture, can contribute to copper pollution through waste disposal.

Functional groups

  • Hydroxyl

  • amine

  • sulfonyl

  • carbonyl

  • corboxyl

  • phenolic and alcoholic hydroxyl

  • methoxyl

  • Phosphate

  • imidazole

  • sulfhydryl

  • sulfate

Methods of application

  • Semipermeable cellulose membrane capsule

  • Dried biomass (living)

  • Dried biomass (immobilised)

  • polyvinyl alcohol (PVA)-sodium alginate (SA) beads

  • Fe(III) hydroxide-coated biomass

  • nFe(III) oxide-coated biomass (nano)

Immobilization matrix

  • Calcium alginate

  • Polyacrylamide gel

  • Silica

Fun Facts and Theories

Fungal cell wall polysaccharides and proteins

  • β-1,3-D-glucan (encoded by genes FKS1 and FKS2)

  • β-1,6-glucan 

  • α-1,3-glucan (synthesised by α-glucan synthase (AGS1).

  • Melanin (1, 8-dihydroxynaphthalene (DHN) intermediate and from L-3, 4-dihydroxyphenylalanine (L-dopa)

  • chitin (synthesised from n-acetylglucosamine by the enzyme chitin synthase)

  • Mannan 

  • Glucuronoxylomannan (GXM)

  • phospholipids 

  • mannoproteins 

  • Chitosan 

 In 2021 fu et al demonstrated that the combined application of Glomus coronatum, an Arbuscular Mycorrhizal Fungi (AMF), and earthworms significantly increased the biomass of plant shoots and roots, reaching a total increase of 100%. Additionally, the combination treatment augmented Cu extraction by T. patula, achieving a remarkable 270% increase compared to the untreated plant. The combined treatment markedly improved the cation exchange capacity, contents of organic matter, and available Cu, P and K. In addition to improving the growth of T. patula and effectively removing copper, the combination treatment supported the regeneration of soil microbial communities which surged in abundance and diversity. Among those to grow abundantly were Bacteroides, Proteobacteria, and Actinobacteria, with the genera Flavobacterium, Pedobacter, Algoriphagus, Gaetbulibacter, Pseudomonas, Luteimonas, and Arthrobacter dominating.

Enzymes

  • metallothionein (MT)

  • glutathionee (GSH)

  • phytochelatins(PCs)

  • plastocyanin

  • 3,4-dihydroxyphenylalanine (DOPA)-melanin

  • Aryl alcohol oxidase

  • catalase

  • oxalate decarboxylase 2

  • copper resistance P-type ATPase pump

Processes:

  • adsorption

  • absorption

  • bioaccumulation

  • ion exchange

  • Intracellular accumulation by transfer across the cell membrane

  • Detoxification by extracellular polymeric substances

  • surface adsorption

Copper is a naturally occurring macronutrient required by flora for growth, reproduction, nutrient acquisition and hormone regulation. Plants are built with various mechanisms designed to extract copper from the soil, leaving them exposed, in the excessive presence of copper, to surplus accumulation of the heavy metal. In the presence of copper, plants upregulate genes managing its acquisition and transport, and past a certain point of exposure, these genes struggle to limit Cu uptake. Additionally, copper can hijack Fe-Su clusters by substituting itself for iron. Iron-sulfur groups are required by various metabolic pathways and proteins to function properly. Fe-Su-containing proteins are responsible for the transfer of electrons in order to produce redox potential in mitochondria and chloroplasts. When copper stress and toxicity result in irons replacement by copper, the electron transfer faculties of Fe-Su groups are crippled, disrupting the electron transport chain in mitochondria and chloroplast, causing stunted growth of the plant.

In some fruiting-body-producing species, the pileus (cap) of the mushrooms is known to produce stress factors which contribute to sequestering the accumulated metal ions into their vacuoles.

Some researchers have highlighted a correlation between edibility and bioaccumulation capacity, noting that non-edible species show higher rates of accumulation than their edible counterparts. To offer an example, The ability of Agaricus bisporus, commonly known as the button mushroom, to accumulate Cu sits in the range of 5-107mg/Kg of dry-weight mushroom. Whereas Galerina vittiformis, a much lesser known but equally ubiquitous mushroom, is capable of removing 800mg/Kg of dry-weight mushroom. More data and analysis would be required to validate such a theory, and ultimately it comes down to the physio-chemical properties of the species and strain. but it lends to reason that mushrooms commonly consumed have a weaker propensity for the accumulation of toxic compounds, for if they possessed such an ability, they might easily have been issued a warning label by our ancestors to whom mushrooms made a substantial dietary contribution.

In lab-scale studies testing the mechanisms, variables and efficiency of fungal biomass in the treatment of metal-contaminated soils and solutions, multiple researchers have noted a low-medium biomass dose threshold, beyond which, efficiency sharply decreases. Researchers have cited interference among binding sites as a potential cause for this decline in efficiency.

‘Thus, a decrease in the biosorption capacity might indicate the overlapping or aggregation of binding sites’ (Kahraman et al. 2005)

  1. Soil Contamination: Copper pollution occurs when copper and its compounds are introduced into the soil through various sources such as industrial activities, agricultural practices, or improper disposal of copper-containing waste. Elevated copper levels in the soil surpass the natural background levels, leading to contamination.

  2. Reduced Soil Fertility: Copper pollution can interfere with soil fertility by negatively impacting important soil properties and processes: a. Nutrient Imbalance: High copper concentrations can disrupt the balance of essential nutrients in the soil, such as zinc, iron, and manganese. This interference can lead to nutrient imbalances and deficiencies in plants, affecting their growth and overall health. b. pH Imbalance: Copper pollution can influence soil pH, leading to acidification or alkalization. Changes in soil pH can affect nutrient availability and microbial activity, further impacting plant growth and soil functioning. c. Organic Matter Degradation: Elevated copper levels can inhibit the activity of soil microorganisms responsible for decomposing organic matter. This can result in the reduced availability of nutrients and organic carbon, affecting soil structure and fertility.

  3. Impaired Microbial Activity: Copper pollution can have toxic effects on soil microorganisms, disrupting their populations and activities: a. Reduced Microbial Diversity: High copper levels can reduce the diversity and abundance of soil microorganisms, including bacteria, fungi, and archaea. This loss of microbial diversity can disrupt important soil processes and nutrient cycling. b. Enzyme Inhibition: Copper toxicity can inhibit the activity of soil enzymes involved in organic matter decomposition, nutrient cycling, and plant-microbe interactions. This can impair important soil functions and nutrient availability for plants.

  4. Inhibition of Plant Growth and Development: Excessive copper in the soil can directly impact plant health and growth: a. Reduced Seed Germination: Copper pollution can inhibit seed germination or delay the process, leading to poor plant establishment and reduced crop productivity. b. Root Damage: High copper levels in the soil can cause damage to plant roots, resulting in reduced nutrient uptake, stunted growth, and physiological disorders. c. Altered Nutrient Uptake: Copper toxicity can disrupt the uptake and utilization of essential nutrients by plants, leading to nutrient deficiencies and imbalances.

Aquatic Species:

  1. Rainbow Trout (Oncorhynchus mykiss)

  2. Atlantic Salmon (Salmo salar)

  3. Bluegill Sunfish (Lepomis macrochirus)

  4. Common Carp (Cyprinus carpio)

  5. Freshwater Mussels (Unionidae family)

  6. Water Fleas (Daphnia spp.)

  7. Amphipods (Gammarus spp.)

  8. Zooplankton (Copepods)

  9. Macroalgae (e.g., Fucus spp., Ulva spp.)

  10. Microalgae (e.g., Chlorella spp., Dunaliella spp.)

  • Agri-Food and Biosciences Institute. (2016). AFBI warns about the risk of chronic copper poisoning in sheep. [online] Available at: https://www.afbini.gov.uk/news/afbi-warns-about-risk-chronic-copper-poisoning-sheep.

    Brancato, M.S., Milonas, L., Bowlby, C.E., Jameson, R. and Davis, J.W. (2009). Marine Sanctuaries Conservation Series (ONMS-09-01) Chemical Contaminants, Pathogen Exposure and General Health Status of Live and Beach-Cast Washington Sea Otters (Enhydra lutris kenyoni). [online] Available at: https://nmssanctuaries.blob.core.windows.net/sanctuaries-prod/media/archive/science/conservation/pdfs/brancato.pdf.

    Hill, G.M. and Shannon, M.C. (2019). Copper and Zinc Nutritional Issues for Agricultural Animal Production. Biological Trace Element Research, [online] 188(1), pp.148–159. doi:https://doi.org/10.1007/s12011-018-1578-5.

    King, K.A., Leleux, J. and Mulhern, B.M. (1984). Molybdenum and Copper Levels in White-Tailed Deer Near Uranium Mines in Texas. The Journal of Wildlife Management, 48(1), p.267. doi:https://doi.org/10.2307/3808486.

    Poppenga, R.H., Ramsey, J., Gonzales, B.J. and Christine Cole Johnson (2012). Reference intervals for mineral concentrations in whole blood and serum of bighorn sheep (Ovis canadensis) in California. 24(3), pp.531–538. doi:https://doi.org/10.1177/1040638712441936.

    Quevedo, L.S., Casagrande, R.A., Costa, L.S., Withoeft, J.A., Mendes, R.P., Avila, G.M., Vavassori, M. and Fonteque, J.H. (2022). Atypical chronic copper poisoning in a sheep secondary to copper wire ingestion - case report. Arquivo Brasileiro de Medicina Veterinária e Zootecnia, 74(4), pp.701–706. doi:https://doi.org/10.1590/1678-4162-12749.

  • Ashpole, S.L., Bishop, C.A. and Elliott, J.E. (2011). Unexplained Die-Off of Larval Barred Tiger Salamanders (ambystoma Mavortium) in an Agricultural Pond in the South Okanagan Valley, British Columbia, Canada. Northwestern Naturalist, [online] 92(3), pp.221–224. Available at: https://www.jstor.org/stable/41300903 [Accessed 9 Jun. 2023].

    Azizishirazi, A., Klemish, J.L. and Pyle, G.G. (2021). Sensitivity of Amphibians to Copper. Environmental Toxicology and Chemistry, 40(7), pp.1808–1819. doi:https://doi.org/10.1002/etc.5049.

    Brown, M.G., Dobbs, E.K., Snodgrass, J.W. and Ownby, D.R. (2012). Ameliorative effects of sodium chloride on acute copper toxicity among Cope’s gray tree frog (Hyla chrysoscelis) and green frog (Rana clamitans) embryos. Environmental Toxicology and Chemistry, 31(4), pp.836–842. doi:https://doi.org/10.1002/etc.1751.

    Calfee, R.D. and Little, E.E. (2017). Toxicity of Cadmium, Copper, and Zinc to the Threatened Chiricahua Leopard Frog (Lithobates [Rana] chiricahuensis). Bulletin of Environmental Contamination and Toxicology, 99(6), pp.679–683. doi:https://doi.org/10.1007/s00128-017-2188-1.

    Chagas, B.R.C., Utsunomiya, H.S.M., Fernandes, M.N. and Carvalho, C.S. (2020). Metabolic responses in bullfrog, Lithobates catesbeianus after exposure to zinc, copper and cadmium. Comparative Biochemistry and Physiology Part C: Toxicology & Pharmacology, [online] 233, p.108768. doi:https://doi.org/10.1016/j.cbpc.2020.108768.

    Fryday, S. and Thompson, H. (2012). Toxicity of pesticides to aquatic and terrestrial life stages of amphibians and occurrence, habitat use and exposure of amphibian species in agricultural environments. EFSA Supporting Publications, 9(9). doi:https://doi.org/10.2903/sp.efsa.2012.en-343.

    Hayes, M. p., Wheeler, C.A., Lind, A.J., Green, G.A. and Macfarlane, D.C. (2016). United States Department of Agriculture Forest Service Pacific Southwest Research Station Foothill Yellow-Legged Frog Conservation Assessment in California. [online] Available at: https://www.fs.usda.gov/psw/publications/documents/psw_gtr248/psw_gtr248.pdf [Accessed 9 Jun. 2023].

    Huang, C.-C., Xu, Y., Briggler, J.T., McKee, M., Nam, P. and Huang, Y. (2010). Heavy metals, hematology, plasma chemistry, and parasites in adult hellbenders (Cryptobranchus alleganiensis). Environmental Toxicology and Chemistry, p.n/a-n/a. doi:https://doi.org/10.1002/etc.148.

    Lance, S.L., Erickson, M.R., Flynn, R.W., Mills, G.L., Tuberville, T.D. and Scott, D.E. (2012). Effects of chronic copper exposure on development and survival in the southern leopard frog (Lithobates [Rana] sphenocephalus). Environmental Toxicology and Chemistry, 31(7), pp.1587–1594. doi:https://doi.org/10.1002/etc.1849.

    Leduc, J., Echaubard, P., Trudeau, V. and Lesbarrères, D. (2016). Copper and nickel effects on survival and growth of northern leopard frog (Lithobates pipiens) tadpoles in field-collected smelting effluent water. Environmental Toxicology and Chemistry, 35(3), pp.687–694. doi:https://doi.org/10.1002/etc.3227.

    Peles, J.D. (2013). Effects of chronic aluminum and copper exposure on growth and development of wood frog (Rana sylvatica) larvae. Aquatic Toxicology, 140-141, pp.242–248. doi:https://doi.org/10.1016/j.aquatox.2013.06.009.

    TY - BOOK AU - Dmitrieva, Elena PY - 2018/11/19 SP - T1 - Effects Of High Copper Exposure On Development And Survival During Early Ontogenesis In The Common Toad DO - 10.1101/471466 ER-

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Mammals:

  1. Bighorn Sheep (Ovis canadensis): Bighorn sheep grazing in areas contaminated with copper have been found to accumulate high copper levels in their liver and kidneys, leading to organ damage and impaired health.

  2. White-tailed Deer (Odocoileus virginianus): Copper pollution in water sources has been associated with elevated copper levels in white-tailed deer, causing liver damage and negatively impacting their overall health and reproductive success.

  3. Sea Otter (Enhydra lutris): In coastal areas impacted by copper pollution, sea otters have been found to experience toxic effects, including liver damage and impaired immune function, which can ultimately lead to population decline.

Amphibians:

  1. Pacific Tree Frog (Pseudacris regilla): Exposure to copper has been shown to affect the development and survival of Pacific tree frog tadpoles. High copper concentrations in water can lead to deformities, reduced growth, and increased mortality in tadpoles.

  2. Northern Leopard Frog (Lithobates pipiens): Copper pollution has been linked to impaired growth, development, and survival of Northern leopard frog tadpoles. Elevated copper levels in water can disrupt their normal physiological processes and lead to negative impacts on their populations.

  3. Common Toad (Bufo bufo): Copper contamination in aquatic habitats has been associated with reduced reproductive success and increased mortality in common toad populations. Copper exposure can disrupt their breeding behavior, embryo development, and overall population viability.

  4. American Bullfrog (Lithobates catesbeianus)

  5. Red-legged Frog (Rana aurora)

  6. Sierra Nevada Yellow-legged Frog (Rana sierrae)

  7. Wood Frog (Lithobates sylvaticus)

  8. Tiger Salamander (Ambystoma tigrinum)

  9. California Red-legged Frog (Rana draytonii)

  10. Hellbender (Cryptobranchus alleganiensis)

  1. Macrocystis pyrifera

  2. Undaria pinnatifida

  1. DNA Strand Breaks: Copper ions can induce DNA strand breaks through oxidative damage. For instance, a study conducted on human lymphocytes exposed to copper sulfate demonstrated increased DNA strand breaks, which were attributed to the generation of reactive oxygen species (ROS) and the subsequent oxidative stress caused by copper.

  2. Oxidative DNA Damage: Copper can catalyze the production of hydroxyl radicals, potent oxidizing agents, which can attack DNA and cause oxidative damage. One specific example is the formation of 8-oxoguanine, an oxidized form of the DNA base guanine. Copper-mediated oxidation of guanine can lead to the accumulation of 8-oxoguanine lesions in DNA, which are associated with mutagenesis and carcinogenesis.

  3. DNA-Protein Crosslinking: Copper can form complexes with proteins that can crosslink to DNA, thereby impairing DNA structure and function. A study investigating copper-induced DNA-protein crosslinking in yeast cells found that copper exposure led to the formation of covalent bonds between copper ions, DNA, and protein molecules, resulting in DNA-protein adducts and hindering DNA repair processes.

  4. Inhibition of DNA Repair: Copper ions can interfere with DNA repair mechanisms by inhibiting the activity of DNA repair enzymes. For example, copper has been shown to inhibit the activity of DNA ligases, which are crucial for sealing DNA strand breaks during DNA repair processes. This inhibition can impede the proper repair of damaged DNA and increase the susceptibility to mutations.

  5. Alteration of DNA Structure: Copper can bind to DNA molecules, leading to changes in DNA conformation and stability. This can affect DNA-protein interactions, transcriptional regulation, and DNA replication. A study investigating the interaction between copper and DNA using spectroscopic techniques revealed changes in the DNA structure, including alterations in DNA base stacking and helical conformation, upon copper binding.

Enzyme Inhibition:

  • Urease: Urease is an enzyme responsible for the hydrolysis of urea into ammonia and carbon dioxide. Copper toxicity can inhibit urease activity in soil, reducing the conversion of urea into plant-available forms of nitrogen, which can result in nitrogen deficiency for plants.

  • Phosphatase: Phosphatase enzymes play a crucial role in the mineralization of organic phosphorus in soil, making it available for plant uptake. Copper pollution can inhibit phosphatase activity, leading to reduced phosphorus availability and impacting plant growth and productivity.

  • β-Glucosidase: β-Glucosidase is involved in the breakdown of complex organic compounds, specifically the hydrolysis of β-glucosides. Copper toxicity can inhibit β-glucosidase activity, impairing the decomposition of organic matter and reducing nutrient cycling in the soil.

    Structural Alteration:

  • Laccase: Laccases are copper-containing enzymes involved in the degradation of lignin, a complex organic polymer found in plant tissues. While copper is an essential cofactor for laccase activity, excessive copper levels can lead to structural changes in the enzyme, altering its efficiency and stability. This can impact the decomposition of lignin-rich organic matter in the soil.

  • Superoxide Dismutase (SOD): SOD is an enzyme that plays a crucial role in antioxidant defense by converting superoxide radicals into less harmful molecules. Copper ions can directly interact with the active site of SOD enzymes, leading to conformational changes and decreased enzyme activity. This can disrupt the antioxidant defense system in soil microorganisms, making them more susceptible to oxidative stress.