Abstract
The total dissolved copper (Cu) concentrations, chemical speciation, and intensities of humic-like fluorescent dissolved organic matter (FDOMH) components were determined in the Nakdong River Estuary. The concentrations of total dissolved Cu ranged from 4.6 to 13.3 nM and showed an inverse correlation with salinity (R2 = 0.93), indicating a conservative mixing trend in the Nakdong River Estuary. The chemical speciation of dissolved Cu was determined by competitive ligand equilibrium adsorptive cathodic stripping voltammetry, and speciation parameters were calculated using ProMCC software. The concentrations of the strong Cu-binding organic ligands (L1) ranged from 3.1 to 96 nM, whereas those of the weak ligand (L2) ranged from 10 to 3400 nM. Both L1 and L2 concentrations were relatively high at the upper sampling sites (river water sites) and decreased in proximity to the coastal sea, indicating that Cu-binding organic ligands from terrestrial sources may be dominant in the Nakdong River Estuary. Although Cu-binding organic ligands showed positive correlations with FDOMH, anomalously high concentrations of Cu-binding organic ligands were observed at river water sites, suggesting additional sources of organic ligands. Our results suggest that Cu-binding organic ligands originated from various sources in estuarine environments.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Data availability
The dataset presented in this study can be found in the manuscript (Table 1).
References
Ahn JM, Lyu S (2017) Analysis of the coordinated operation of reservoirs and weirs during the management of Nakdong River water resources. J Water Resour Plan Manag 143(8):04017030. https://doi.org/10.1061/(ASCE)WR.1943-5452.0000780
Apte SC, Gardner MJ, Ravenscroft JE (1990) An investigation of copper complexation in the Severn Estuary using differential pulse cathodic stripping voltammetry. Mar Chem 29:63–75. https://doi.org/10.1016/0304-4203(90)90006-X
Beck AJ, Cochran JK, Sañudo-Wilhelmy SA (2009) Temporal trends of dissolved trace metals in Jamaica Bay, NY: importance of wastewater input and submarine groundwater discharge in an urban estuary. Estuaries Coast 32(3):535–550. https://doi.org/10.1007/s12237-009-9140-5
Boyle EA, Huested SS, Grant B (1982) The chemical mass balance of the amazon plume-II. Copper, nickel, and cadmium. Deep Sea Res A 29(11):1355–1364. https://doi.org/10.1016/0198-0149(82)90013-9
Brand LE, Sunda WG, Guillard RRL (1986) Reduction of marine phytoplankton reproduction rates by copper and cadmium. J Exp Mar Biol Ecol 96(3):225–250. https://doi.org/10.1016/0022-0981(86)90205-4
Bro R (1997) PARAFAC. Tutorial and applications. Chemometr Intell Lab Syst 38(2):149–171. https://doi.org/10.1016/S0169-7439(97)00032-4
Bruland KW, Lohan MC (2006) Controls of trace metals in seawater. In: Elderfield H (ed) The oceans and marine geochemistry, 1st edn. Elsevier, pp 23–47
Buck KN, Bruland KW (2005) Copper speciation in San Francisco Bay: a novel approach using multiple analytical windows. Mar Chem 96(1–2):185–198. https://doi.org/10.1016/j.marchem.2005.01.001
Carlson CA, Hansell DA (2015) DOM sources, sinks, reactivity, and budgets. In: Hansell DA, Carlson CA (eds) Biogeochemistry of marine dissolved organic matter, 2nd edn. Elsevier, pp 65–126
Chapman CS, Capodaglio G, Turetta C, van den Berg CMG (2009) Benthic fluxes of copper, complexing ligands and thiol compounds in shallow lagoon waters. Mar Environ Res 67(1):17–24. https://doi.org/10.1016/j.marenvres.2008.07.010
Chen X, Seo H, Han H, Seo J, Kim T, Kim G (2021) Conservative behavior of terrestrial trace elements associated with humic substances in the coastal ocean. Geochim Cosmochim Acta 308:373–383. https://doi.org/10.1016/j.gca.2021.05.020
Coble PG (2007) Marine optical biogeochemistry: the chemistry of ocean color. Chem Rev 107(2):402–418. https://doi.org/10.1021/cr050350+
Deycard VN, Schäfer J, Blanc G, Coynel A, Petit JCJ, Lanceleur L, Dutruch L, Bossy C, Ventura A (2014) Contributions and potential impacts of seven priority substances (As, Cd, Cu, Cr, Ni, Pb, and Zn) to a major European Estuary (Gironde Estuary, France) from urban wastewater. Mar Chem 167:123–134. https://doi.org/10.1016/j.marchem.2014.05.005
Dowell WH (1985) Kinetics and mechanisms of dissolved organic carbon retention in a headwater stream. Biogeochemistry 1(4):329–352. https://doi.org/10.1007/BF02187376
Dupont CL, Ahner BA (2005) Effects of copper, cadmium, and zinc on the production and exudation of thiols by Emiliania huxleyi. Limnol Oceanogr 50(2):508–515. https://doi.org/10.4319/lo.2005.50.2.0508
Durán I, Beiras R (2013) Ecotoxicologically based marine acute water quality criteria for metals intended for protection of coastal areas. Sci Total Environ 463:446–453. https://doi.org/10.1016/j.scitotenv.2013.05.077
Guo W, Yang L, Hong H, Stedmon CA, Wang F, Xu J, Xie Y (2011) Assessing the dynamics of chromophoric dissolved organic matter in a subtropical estuary using parallel factor analysis. Mar Chem 124(1–4):125–133. https://doi.org/10.1016/j.marchem.2011.01.003
Jacquot JE, Horak RE, Amin SA, Devol AH, Ingalls AE, Armbrust EV, Stahl DA, Moffett JW (2014) Assessment of the potential for copper limitation of ammonia oxidation by Archaea in a dynamic estuary. Mar Chem 162:37–49. https://doi.org/10.1016/j.marchem.2014.02.002
Jeong KS, Kim DK, Joo GJ (2007) Delayed influence of dam storage and discharge on the determination of seasonal proliferations of Microcystis aeruginosa and Stephanodiscus hantzschii in a regulated river system of the lower Nakdong River (South Korea). Water Res 41(6):1269–1279. https://doi.org/10.1016/j.watres.2006.11.054
Kim J, Cho HM, Kim G (2018) Significant production of humic fluorescent dissolved organic matter in the continental shelf waters of the northwestern Pacific Ocean. Sci Rep 8(1):1–8. https://doi.org/10.1038/s41598-018-23299-1
Kim T, Kim H, Kim G (2020) Tracing river water versus wastewater sources of trace elements using rare earth elements in the Nakdong River estuarine waters. Mar Pollut Bull 160:111589. https://doi.org/10.1016/j.marpolbul.2020.111589
Kogut MB, Voelker BM (2001) Strong copper-binding behavior of terrestrial humic substances in seawater. J Environ Sci Technol 35(6):1149–1156. https://doi.org/10.1021/es0014584
Kothawala DN, Murphy KR, Stedmon CA, Weyhenmeyer GA, Tranvik LJ (2013) Inner filter correction of dissolved organic matter fluorescence. Limnol Oceanogr-Meth 11(12):616–630. https://doi.org/10.4319/lom.2013.11.616
Laglera LM, van den Berg CMG (2006) Photochemical oxidation of thiols and copper complexing ligands in estuarine waters. Mar Chem 101(1–2):130–140. https://doi.org/10.1016/j.marchem.2006.01.006
Lawaetz AJ, Stedmon CA (2009) Fluorescence intensity calibration using the Raman scatter peak of water. Appl Spectrosc 63(8):936–940. https://doi.org/10.1366/000370209788964548
Leal MFC, van den Berg CMG (1998) Evidence for strong copper(I) complexation by organic ligands in seawater. Aquat Geochem 4(1):49–75. https://doi.org/10.1023/A:1009653002399
Lee SA, Kim G (2018) Sources, fluxes, and behaviors of fluorescent dissolved organic matter (FDOM) in the Nakdong River Estuary. Korea Biogeosci 15(4):1115–1122. https://doi.org/10.5194/bg-15-1115-2018
Maldonado MT, Allen AE, Chong JS, Lin K, Leus D, Karpenko N, Harris SL (2006) Copper-dependent iron transport in coastal and oceanic diatoms. Limnol Oceanogr 51(4):1729–1743. https://doi.org/10.4319/lo.2006.51.4.1729
Moffett JW, Brand LE (1996) Production of strong extracellular cu chelators by marine cyanobacteria in response to cu stress. Limnol Oceanogr 41(3):388–395. https://doi.org/10.4319/lo.1996.41.3.0388
Moffett JW, Dupont C (2007) Cu complexation by organic ligands in the sub-arctic NW Pacific and Bering Sea. Deep Sea Res Pt I 54(4):586–595. https://doi.org/10.1016/j.dsr.2006.12.013
Moffett JW, Brand LE, Croot PL, Barbeau KA (1997) Cu speciation and cyanobacterial distribution in harbors subject to anthropogenic Cu inputs. Limnol Oceanogr 42(5):789–799. https://doi.org/10.4319/lo.1997.42.5.0789
Murphy KR, Stedmon CA, Wenig P, Bro R (2014) OpenFluor–an online spectral library of auto-fluorescence by organic compounds in the environment. Anal Methods 6(3):658–661. https://doi.org/10.1039/C3AY41935E
Omanović D, Garnier C, Pižeta I (2015) ProMCC: an all-in-one tool for trace metal complexation studies. Mar Chem 173:25–39. https://doi.org/10.1016/j.marchem.2014.10.011
Peers G, Quesnel SA, Price NM (2005) Copper requirements for iron acquisition and growth of coastal and oceanic diatoms. Limnol Oceanogr 50(4):1149–1158. https://doi.org/10.4319/lo.2005.50.4.1149
Qualls RG, Haines BL, Swank WT (1991) Fluxes of dissolved organic nutrients and humic substances in a deciduous forest. Ecology 72(1):254–266. https://doi.org/10.2307/1938919
Rapp I, Schlosser C, Rusiecka D, Gledhill M, Achterberg EP (2017) Automated preconcentration of Fe, Zn, Cu, Ni, Cd, Pb Co, and Mn in seawater with analysis using high-resolution sector field inductively-coupled plasma mass spectrometry. Anal Chim Acta 976:1–13. https://doi.org/10.1016/j.aca.2017.05.008
Santos-Echeandía J, Laglera LM, Prego R, van den Berg CMG (2008) Copper speciation in estuarine waters by forward and reverse titrations. Mar Chem 108(3–4):148–158. https://doi.org/10.1016/j.marchem.2007.11.004
Semeniuk DM, Bundy RM, Payne CD, Barbeau KA, Maldonado MT (2015) Acquisition of organically complexed copper by marine phytoplankton and bacteria in the northeast subarctic Pacific Ocean. Mar Chem 173:222–233. https://doi.org/10.1016/j.marchem.2015.01.005
Shank GC, Whitehead RF, Smith ML, Skrabal SA, Kieber RJ (2006) Photodegradation of strong copper-complexing ligands in organic-rich estuarine waters. Limnol Oceanogr 51(2):884–892. https://doi.org/10.4319/lo.2006.51.2.0884
Shiller AM, Boyle EA (1991) Trace elements in the Mississippi River Delta outflow region: behavior at high discharge. Geochim Cosmochim Acta 55(11):3241–3251. https://doi.org/10.1016/0016-7037(91)90486-O
Skrabal SA, Donat JR, Burdige DJ (2000) Pore water distributions of dissolved copper and copper-complexing ligands in estuarine and coastal marine sediments. Geochim Cosmochim Acta 64(11):1843–1857. https://doi.org/10.1016/S0016-7037(99)00387-7
Stedmon CA, Bro R (2008) Characterizing dissolved organic matter fluorescence with parallel factor analysis: a tutorial. Limnol Oceanogr-Meth 6(11):572–579. https://doi.org/10.4319/lom.2008.6.572
Stedmon CA, Markager S, Bro R (2003) Tracing dissolved organic matter in aquatic environments using a new approach to fluorescence spectroscopy. Mar Chem 82(3–4):239–254. https://doi.org/10.1016/S0304-4203(03)00072-0
Sunda WG, Huntsman SA (1998) Interactions among Cu2+, Zn2+, and Mn2+ in controlling cellular Mn, Zn, and growth rate in the coastal alga Chlamydomonas. Limnol Oceanogr 43(6):1055–1064. https://doi.org/10.4319/lo.1998.43.6.1055
Tang D, Shafer MM, Karner DA, Overdier J, Armstrong DE (2004) Factors affecting the presence of dissolved glutathione in estuarine waters. Environ Sci Technol 38(16):4247–4253. https://doi.org/10.1021/es030669g
van den Berg CMG (1984) Determination of the complexing capacity and conditional stability constants of complexes of copper(II) with natural organic ligands in seawater by cathodic stripping voltammetry of copper-catechol complex ions. Mar Chem 15(1):1–18. https://doi.org/10.1016/0304-4203(84)90035-5
van den Berg CMG, Merks AGA, Duursma EK (1987) Organic ocomplexation and its control of the dissolved concentrations of copper and zinc in the Scheldt estuary. Estuar Coast Shelf Sci 24(6): 785–797. https://doi.org/10.1016/0272-7714(87)90152-1
Wang D, Lin W, Yang X, Zhai W, Dai M, Chen CTA (2012) Occurrences of dissolved trace metals (Cu, Cd, and Mn) in the Pearl River Estuary (China), a large river-groundwater-estuary system. Cont Shelf Res 50–51:54–63. https://doi.org/10.1016/j.csr.2012.10.009
Wang ZL, Liu CQ (2003) Distribution and partition behavior of heavy metals between dissolved and acid-soluble fractions along a salinity gradient in the Changjiang Estuary, eastern China. Chem Geol 202(3–4):383–396. https://doi.org/10.1016/j.chemgeo.2002.05.001
Whitby H, Hollibaugh JT, van den Berg CMG (2017) Chemical speciation of copper in a salt marsh estuary and bioavailability to Thaumarchaeota. Front Mar Sci 4:1–15. https://doi.org/10.3389/fmars.2017.00178
Wong KH, Obata H, Kim T, Mashio AS, Fukuda H, Ogawa H (2018) Organic complexation of copper in estuarine water: an assessment of the multi-detection window approach. Mar Chem 204:144–151. https://doi.org/10.1016/j.marchem.2018.07.001
Wong KH, Obata H, Kim T, Wakuta Y, Takeda S (2019) Distribution and speciation of copper and its relationship with FDOM in the East China Sea. Mar Chem 212:96–107. https://doi.org/10.1016/j.marchem.2019.04.005
Zepp RG, Sheldon WM, Moran MA (2004) Dissolved organic fluorophores in southeastern US coastal waters: correction method for eliminating Rayleigh and Raman scattering peaks in excitation–emission matrices. Mar Chem 89(1–4):15–36. https://doi.org/10.1016/jmarchem.2004.02.006
Acknowledgements
This research was supported by the National Research Foundation of Korea [NRF-2019R1G1A1099394 and NRF-2020R1C1C1008964].
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Sim, H., Lim, I., Kim, J. et al. Chemical Speciation of Dissolved Copper in the Nakdong River Estuary and Its Relationship with Humic-Like Fluorescent Dissolved Organic Matter. Ocean Sci. J. 58, 4 (2023). https://doi.org/10.1007/s12601-022-00098-4
Received:
Revised:
Accepted:
Published:
DOI: https://doi.org/10.1007/s12601-022-00098-4