Geochemical factors affecting the solubility of copper in seawater
Brad M. Angel
A C , Simon C. Apte A , Graeme E. Batley A and Mark Raven B
+ Author Affiliations
- Author Affiliations
A CSIRO Land and Water, Locked Bag 2007, Kirrawee, NSW 2232, Australia.
B CSIRO Land and Water, Urrbrae, SA 5064, Australia.
C Corresponding author. Email: brad.angel@csiro.au
Environmental Chemistry 18(1) 1-11 https://doi.org/10.1071/EN20133
Submitted: 15 September 2020 Accepted: 8 November 2020 Published: 27 November 2020
Journal Compilation © CSIRO 2021 Open Access CC BY
Environmental context. Many trace metals, including copper, are only sparingly soluble in seawater and may exist in both dissolved and particulate forms (e.g. as precipitates). Aquatic organisms may experience different toxic effects from exposure to dissolved and particulate trace metals. This study investigates how concentration, reaction time and changes to precipitate composition/mineral formation affect copper solubility in seawater, thus influencing metal bioavailability and toxicity in the field and laboratory.
Abstract. A lack of knowledge on the solubility of metals such as copper affects the ability to predict the forms (dissolved and particulate) that organisms are exposed to in field and laboratory waters. Laboratory tests were conducted where copper (total concentrations of 0.5 to 20 mg L−1) was added to natural and artificial seawater (pH 8.15, 22 °C), equilibrated for 28 days and dissolved copper monitored at periodic intervals. At 0.5 mg L−1, dissolved copper concentrations remained stable over 28 days and no precipitates were detected. However, at higher total copper concentrations, an initial rapid precipitation phase was followed by the establishment of a metastable equilibrium that persisted for periods of days to weeks, and whose solubility concentrations and duration were influenced by the total copper concentration and typically in the range 0.6 to 0.9 mg L−1. After 5 to 15 days, a step change decrease in dissolved copper concentration followed by a slow decline was observed in the >2 mg L−1 total copper treatments. The minimum solubility measured after 28 days was 0.053 mg L−1. Elemental and X-ray diffraction analyses indicated that the copper precipitates comprised similar proportions of amorphous copper hydroxycarbonate and amorphous dicopper trihydroxide chloride after 1 day and transformed to predominantly mineralised dicopper trihydroxide chloride in the clinoatacamite polymorph form after 28 days. These observations have particular relevance for toxicity tests of less sensitive organisms and highlight the need to consider metal solubility, exposure to precipitates and changes in precipitate mineral phases.
Keywords: clinoatacamite, concentration, copper, duration, geochemical factors, precipitation, seawater, toxicity.
References
Adeyemi JA, Klerks PL (2012). Salinity acclimation modulates copper toxicity in the sheepshead minnow, Cyprinodon variegatus. Environmental Toxicology and Chemistry 31, 1573–1578.| Salinity acclimation modulates copper toxicity in the sheepshead minnow, Cyprinodon variegatusCrossref | GoogleScholarGoogle Scholar | 22511216PubMed |
Angel BM, Hales LT, Simpson SL, Apte SC, Chariton AA, Shearer DA, Jolley DF (2010a). Spatial variability of cadmium, copper, manganese, nickel and zinc in the Port Curtis Estuary, Queensland, Australia. Marine and Freshwater Research 61, 170–183.
| Spatial variability of cadmium, copper, manganese, nickel and zinc in the Port Curtis Estuary, Queensland, AustraliaCrossref | GoogleScholarGoogle Scholar |
Angel BM, Simpson SL, Jolley DF (2010b). Toxicity to Melita plumulosa from intermittent and continuous exposures to dissolved copper. Environmental Toxicology and Chemistry 29, 2823–2830.
| Toxicity to Melita plumulosa from intermittent and continuous exposures to dissolved copperCrossref | GoogleScholarGoogle Scholar | 20836070PubMed |
Angel BM, Apte SC, Batley GE, Golding LA (2016a). Geochemical controls on aluminium concentrations in coastal waters. Environmental Chemistry 13, 111–118.
| Geochemical controls on aluminium concentrations in coastal watersCrossref | GoogleScholarGoogle Scholar |
Angel BM, Apte SC, Batley GE, Raven MD (2016b). Lead solubility in seawater: an experimental study. Environmental Chemistry 13, 489–495.
| Lead solubility in seawater: an experimental studyCrossref | GoogleScholarGoogle Scholar |
Apte SC, Day GM (1998). Dissolved metal concentrations in the Torres Strait and Gulf of Papua. Marine Pollution Bulletin 36, 298–304.
| Dissolved metal concentrations in the Torres Strait and Gulf of PapuaCrossref | GoogleScholarGoogle Scholar |
Bambang Y, Thuet P, Charmantier-Daures M, Trilles J-P, Charmantier G (1995). Effect of copper on survival and osmoregulation of various developmental stages of the shrimp Penaeus japonicus bate (Crustacea, Decapoda). Aquatic Toxicology 33, 125–139.
| Effect of copper on survival and osmoregulation of various developmental stages of the shrimp Penaeus japonicus bate (Crustacea, Decapoda)Crossref | GoogleScholarGoogle Scholar |
Bianchi G, Longhi P (1973). Copper in seawater, potential–pH diagrams. Corrosion Science 13, 853–864.
| Copper in seawater, potential–pH diagramsCrossref | GoogleScholarGoogle Scholar |
Burton DT, Fisher DJ (1990). Acute toxicity of cadmium, copper, zinc, ammonia, 3,3′-dichlorobenzidine, 2,6-dichloro-4-nitroaniline, methylene chloride, and 2,4,6-trichlorophenol to juvenile grass shrimp and killifish. Bulletin of Environmental Contamination and Toxicology 44, 776–783.
| Acute toxicity of cadmium, copper, zinc, ammonia, 3,3′-dichlorobenzidine, 2,6-dichloro-4-nitroaniline, methylene chloride, and 2,4,6-trichlorophenol to juvenile grass shrimp and killifishCrossref | GoogleScholarGoogle Scholar | 2344484PubMed |
Chen J-C, Lin C-H (2001). Toxicity of copper sulfate for survival, growth, molting and feeding of juveniles of the tiger shrimp, Penaeus monodon. Aquaculture 192, 55–65.
| Toxicity of copper sulfate for survival, growth, molting and feeding of juveniles of the tiger shrimp, Penaeus monodonCrossref | GoogleScholarGoogle Scholar |
Donat JR, van den Berg CMG (1992). A new cathodic stripping voltammetric method for determining organic copper complexation in seawater. Marine Chemistry 38, 69–90.
| A new cathodic stripping voltammetric method for determining organic copper complexation in seawaterCrossref | GoogleScholarGoogle Scholar |
Frimmel FH, Huber L (1996). Influence of humic substances on the aquatic adsorption of heavy metals on defined mineral phases. Environment International 22, 507–517.
| Influence of humic substances on the aquatic adsorption of heavy metals on defined mineral phasesCrossref | GoogleScholarGoogle Scholar |
Füredi-Milhofer H (1980). Investigations of complex precipitation systems. Croatica Chemica Acta 53, 243–254.
Furuta T, Iwata N, Kikuchi K (2008). Effects of fish size and water temperature on the acute toxicity of copper for Japanese flounder, Paralichthys olivaceus, and Red Sea bream, Pagrus major. Journal of the World Aquaculture Society 39, 766–773.
| Effects of fish size and water temperature on the acute toxicity of copper for Japanese flounder, Paralichthys olivaceus, and Red Sea bream, Pagrus majorCrossref | GoogleScholarGoogle Scholar |
Gaulier C, Zhou C, Guo W, Bratkic A, Superville P-J, Billon G, Baeyens W, Gao Y (2019). Trace metal speciation in North Sea coastal waters. The Science of the Total Environment 692, 701–712.
| Trace metal speciation in North Sea coastal watersCrossref | GoogleScholarGoogle Scholar | 31539978PubMed |
Golding LA, Angel BM, Batley GE, Apte SC, Krassoi R, Doyle CJ (2015). Derivation of a water quality guideline for aluminium in marine waters. Environmental Toxicology and Chemistry 34, 141–151.
| Derivation of a water quality guideline for aluminium in marine watersCrossref | GoogleScholarGoogle Scholar | 25318392PubMed |
Grice JD, Szymanski JT, Jambor JL (1996). Crystal structure of clinoatacamite, a new polymorph of Cu2(OH)3Cl. Canadian Mineralogist 34, 73–78.
Gustafsson JP (2015). Visual Minteq ver. 3.1. Available at http://vminteq.lwr.kth.se [Verified 14 May 2015]
Hannington MD (1993). The formation of atacamite during weathering of sulfides on the modern sea-floor. Canadian Mineralogist 31, 945–956.
Hidmi L, Edwards M (1999). Role of temperature and pH in Cu(OH)2 solubility. Environmental Science & Technology 33, 2607–2610.
| Role of temperature and pH in Cu(OH)2 solubilityCrossref | GoogleScholarGoogle Scholar |
Hua X, Dong D, Liu L, Gao M, Liang D (2012). Comparison of trace metal adsorption onto different solid materials and their chemical components in a natural aquatic environment. Applied Geochemistry 27, 1005–1012.
| Comparison of trace metal adsorption onto different solid materials and their chemical components in a natural aquatic environmentCrossref | GoogleScholarGoogle Scholar |
Jambor JL, Dutrizac JE, Roberts AC, Grice JD, Szymanski JT (1996). Clinoatacamite, a new polymorph of Cu2(OH)3Cl, and its relationship to paratacamite and ‘anarakite’. Canadian Mineralogist 34, 61–72.
Kester DR, Duedall IW, Connors DN, Pytkowicz RM (1967). Preparation of artificial seawater. Limnology and Oceanography 12, 176–179.
| Preparation of artificial seawaterCrossref | GoogleScholarGoogle Scholar |
Krauskopf KB (1956). Factors controlling the concentration of thirteen trace metals in seawater. Geochimica et Cosmochimica Acta 9, 1–32.
| Factors controlling the concentration of thirteen trace metals in seawaterCrossref | GoogleScholarGoogle Scholar |
Kremling K, Pohl C (1989). Studies on the spatial and seasonal variability of dissolved cadmium, copper and nickel in north-east Atlantic surface waters. Marine Chemistry 27, 43–60.
| Studies on the spatial and seasonal variability of dissolved cadmium, copper and nickel in north-east Atlantic surface watersCrossref | GoogleScholarGoogle Scholar |
Krivovichev SV, Hawthorne FC, Williams PA (2017). Structural complexity and crystallization: the Ostwald sequence of phases in the Cu2(OH)3Cl system (botallackite–atacamite–clinoatacamite). Structural Chemistry 28, 153–159.
| Structural complexity and crystallization: the Ostwald sequence of phases in the Cu2(OH)3Cl system (botallackite–atacamite–clinoatacamite)Crossref | GoogleScholarGoogle Scholar |
Levy JL, Angel BM, Stauber JL, Poon WL, Simpson SL, Cheng SH, Jolley DF (2008). Uptake and internalisation of copper by three marine microalgae: comparison of copper-sensitive and copper-tolerant species. Aquatic Toxicology 89, 82–93.
| Uptake and internalisation of copper by three marine microalgae: comparison of copper-sensitive and copper-tolerant speciesCrossref | GoogleScholarGoogle Scholar | 18639348PubMed |
Li M, Wang LQ, Xia Y, Yang QY (2013). Research on the spectral analysis and stability of copper green. Guangpuxue Yu Guangpu Fenxi 33, 3293–3297.
Lu YF, Allen HE (2006). A predictive model for copper partitioning to suspended particulate matter in river waters. Environmental Pollution 143, 60–72.
| A predictive model for copper partitioning to suspended particulate matter in river watersCrossref | GoogleScholarGoogle Scholar |
Luoma SN, Rainbow PS (2008). Toxicity testing. In ‘Metal contamination in aquatic environments: science and lateral management’. pp. 232–259. (Cambridge University Press: Cambridge)
Ma Y, Rivera-Ingraham G, Nommick A, Bickmeyer U, Roeder T (2020). Copper and cadmium administration induce toxicity and oxidative stress in the marine flatworm Macrostomum lignano. Aquatic Toxicology 221, 105428
| Copper and cadmium administration induce toxicity and oxidative stress in the marine flatworm Macrostomum lignanoCrossref | GoogleScholarGoogle Scholar | 32035411PubMed |
North NA, McLeod ID (1987). Corrosion of metals. In ‘Conservation of marine archaeological objects’. (Ed. C Pearson) Ch. 4, pp. 68–98 (Butterworths: London)
Ohlsson K, Wallmark P (1999). Novel calibration with correction for drift and non-linear response for continuous-flow isotope ratio mass spectrometry applied to the determination of δ15N, total nitrogen, δ13C and total carbon in biological material. Analyst 124, 571–577.
| Novel calibration with correction for drift and non-linear response for continuous-flow isotope ratio mass spectrometry applied to the determination of δ15N, total nitrogen, δ13C and total carbon in biological materialCrossref | GoogleScholarGoogle Scholar |
Pilson MEQ (1998). ‘An introduction to the chemistry of the sea, 2nd edn.’ (Cambridge University Press: London)
Pollard AM, Thomas RG, Williams PA (1989). Synthesis and stabilities of the basic copper(II) chlorides atacamite, paratacamite and botallackite. Mineralogical Magazine 53, 557–563.
| Synthesis and stabilities of the basic copper(II) chlorides atacamite, paratacamite and botallackiteCrossref | GoogleScholarGoogle Scholar |
Pritula I, Sangwal K (2015). Fundamentals of crystal growth from solutions. In ‘Handbook of crystal growth, 2nd edn’. (Ed. P Rudolph) pp. 1185–1227. (Elsevier, BV: Amsterdam)
Savenko VS, Shatalov IA (1998). Atacamite solubilities and the physicochemical state of solute copper in seawater. Geokhimiya 8, 842–847.
Stumm W, Morgan JJ (1996). Precipitation and dissolution. In ‘Aquatic chemistry, chemical equilibria and rates in natural waters, 3rd edn’. pp. 356–357 (John Wiley & Sons, Inc.: New York, NY)
Symes JL, Kester DR (1985). Copper(II) interaction with carbonate species based on malachite solubility in perchorate medium at the ionic strength of seawater. Marine Chemistry 16, 189–211.
| Copper(II) interaction with carbonate species based on malachite solubility in perchorate medium at the ionic strength of seawaterCrossref | GoogleScholarGoogle Scholar |
Valdovinos C, Zuniga M (2002). Copper acute toxicity tests with the sand crab Emerita analoga (Decapoda: Hippidae): a biomonitor of heavy metal pollution in Chilean coastal seawater?. Bulletin of Environmental Contamination and Toxicology 69, 393–400.
| Copper acute toxicity tests with the sand crab Emerita analoga (Decapoda: Hippidae): a biomonitor of heavy metal pollution in Chilean coastal seawater?Crossref | GoogleScholarGoogle Scholar | 12177761PubMed |
Wang F, Chen J, Forsling W (1997). Modeling sorption of trace metals on natural sediments by surface complexation model. Environmental Science & Technology 31, 448–453.
| Modeling sorption of trace metals on natural sediments by surface complexation modelCrossref | GoogleScholarGoogle Scholar |
Wang R-F, Zhu L-M, Zhang J, An X-P, Yang Y-P, Song M, Zhang L (2020). Developmental toxicity of copper in marine medaka (Oryzias melastigma) embryos and larvae. Chemosphere 247, 125923
| Developmental toxicity of copper in marine medaka (Oryzias melastigma) embryos and larvaeCrossref | GoogleScholarGoogle Scholar | 31972495PubMed |
Wong PPK, Chu LM, Wang CK (1999). Study of toxicity and bioaccumulation of copper in the silver sea bream Sparus sarba. Environment International 25, 417–422.
| Study of toxicity and bioaccumulation of copper in the silver sea bream Sparus sarbaCrossref | GoogleScholarGoogle Scholar |
Wu J, Li L, Zhu Z, Zhong J, Su G, Zhou C, Lan K, Fang M (2019). Therapeutic effect of copper sulfate on cryptocaryoniosis in twospot puffer Takifugu bimaculatus. Fisheries Science 38, 305–312.
