Isotopic evolution of dissolved Ni, Cu, and Zn along the Kuroshio through the East China Sea

Araújo, D.F., Ponzevera, E., Weiss, D.J., Knoery, J., Briant, N., Yepez, S., Bruzac, S.,

Sireau, T., Brach-Papa, C., 2021. Application of Zn Isotope Compositions in Oysters

to Monitor and Quantify Anthropogenic Zn Bioaccumulation in Marine

Environments over Four Decades: A “Mussel Watch Program” Upgrade. ACS ES&T

Water 1 (4), 1035–1046.

Archer, C., Vance, D., Milne, A., Lohan, M.C., 2020. The oceanic biogeochemistry of

nickel and its isotopes: new data from the South Atlantic and the Southern Ocean

biogeochemical divide. Earth Planet. Sci. Lett. 535, 116118.

Baconnais, I., Rouxel, O., Dulaquais, G., Boye, M., 2019. Determination of the copper

isotope composition of seawater revisited: a case study from the Mediterranean Sea.

Chem. Geol. 511, 465–480.

Boye, M., et al., 2012. Distributions of dissolved trace metals (Cd, Cu, Mn, Pb, Ag) in the

southeastern Atlantic and the Southern Ocean. Biogeosciences 9 (8), 3231–3246.

Boyle, E.A., Sclater, F.R., Edmond, J.M., 1977. The distribution of dissolved copper in the

Pacific. Earth Planet. Sci. Lett. 37 (1), 38–54.

Brand, L.E., Sunda, W.G., Guillard, R.R.L., 1986. Reduction of marine phytoplankton

reproduction rates by copper and cadmium. J. Exp. Mar. Biol. Ecol. 96 (3), 225–250.

Cameron, V., Vance, D., 2014. Heavy nickel isotope compositions in rivers and the

oceans. Geochim. Cosmochim. Acta 128 (0), 195–211.

Chen, J., Gaillardet, J., Louvat, P., 2008. Zinc Isotopes in the Seine River Waters, France:

A Probe of Anthropogenic Contamination. Environ. Sci. Technol. 42 (17),

6494–6501.

Ciscato, E.R., Bontognali, T.R.R., Vance, D., 2018. Nickel and its isotopes in organic-rich

sediments: implications for oceanic budgets and a potential record of ancient

seawater. Geosciences 494, 239–250.

Conway, T.M., John, S.G., 2014. The biogeochemical cycling of zinc and zinc isotopes in

the North Atlantic Ocean. Glob. Biogeochem. Cycles 28 (10), 1111–1128.

Conway, T.M., John, S.G., 2015. The cycling of iron, zinc and cadmium in the North East

Pacific Ocean – insights from stable isotopes. Geochim. Cosmochim. Acta 164,

262–283.

Croot, P.L., Baars, O., Streu, P., 2011. The distribution of dissolved zinc in the Atlantic

sector of the Southern Ocean. Deep-Sea Res. II Top. Stud. Oceanogr. 58 (25),

2707–2719.

Dong, S., et al., 2017. Isotopic signatures suggest important contributions from recycled

gasoline, road dust and non-exhaust traffic sources for copper, zinc and lead in PM10

in London, United Kingdom. Atmos. Environ. 165, 88–98.

Guinoiseau, D., et al., 2018. Fate of particulate copper and zinc isotopes at the Solim˜

oesNegro river confluence, Amazon Basin, Brazil. Chem. Geol. 489, 1–15.

Guo, Y., Yang, S., 2016. Heavy metal enrichments in the Changjiang (Yangtze River)

catchment and on the inner shelf of the East China Sea over the last 150years. Sci.

Total Environ. 543, 105–115.

Hsu, S.C., et al., 2010. Sources, solubility, and dry deposition of aerosol trace elements

over the East China Sea. Mar. Chem. 120 (1–4), 116–127.

Jiang, S.Y.N., Yang, F., Chan, K.L., Ning, Z., 2014. Water solubility of metals in coarse PM

and PM2.5 in typical urban environment in Hong Kong. Atmospheric. Pollut. Res. 5

(2), 236–244.

5. Conclusions

We revealed the distributions of dissolved Ni, Cu, and Zn and their

isotope ratios in the ECS. The concentrations and isotope ratios of Ni, Cu,

and Zn in deep water of the ECS are almost the same as those in the

western North Pacific, which reflects the inflow of deep water from the

western North Pacific. In the CDW, the concentrations of Ni, Cu, and Zn

are 3.0–4.1 nmol/kg, 2.0–2.7 nmol/kg, and 0.5–1.1 nmol/kg, respec­

tively. These concentrations are higher than those in the North Pacific,

suggesting the supply of these elements from the continent. In the CDW,

δ60Ni ranges from +0.8 to +1.4‰, which is evidently lower than that in

surface water of the Okinawa Trough and the western North Pacific

(1.7‰). The distributions of concentrations and isotope ratios for Ni in

the ECS are explained by simple mixing among the three endmembers

(CDW, KSW, and DW in the western North Pacific). A mixing model

using Ni isotope ratios and concentrations quantitatively evaluates the

sources of dissolved Ni in the ECS. Dissolved Ni in the CDW extends to

subsurface water at the stations along the Kuroshio (AND31 and

AND06), with a maximum of 58% at 30 m depth. In the CDW, δ65Cu

ranges from +0.4 to +0.5‰ and δ66Zn ranges from − 0.1 to +0.2‰,

which are close to those in the surface water of the Okinawa Trough but

lower than those in the surface water of the distal ocean, such as the

central Pacific. Compared with published data from the global ocean,

dissolved Ni, Cu, and Zn are isotopically lighter in the surface water of

some coastal regions than in the pelagic regions, indicating that isoto­

pically light Ni, Cu, and Zn are supplied from the continents.

10

A Self-archived copy in

Kyoto University Research Information Repository

https://repository.kulib.kyoto-u.ac.jp

S. Takano et al.

Marine Chemistry 243 (2022) 104135

Schlitzer, R., et al., 2018. The GEOTRACES intermediate data product 2017. Chem. Geol.

493, 210–223.

Siebert, C., N¨

agler, T.F., Kramers, J.D., 2001. Determination of molybdenum isotope

fractionation by double-spike multicollector inductively coupled plasma mass

spectrometry. Geochem. Geophys. Geosyst. 2 (7).

Souto-Oliveira, C.E., Babinski, M., Araújo, D.F., Andrade, M.F., 2018. Multi-isotopic

fingerprints (Pb, Zn, Cu) applied for urban aerosol source apportionment and

discrimination. Sci. Total Environ. 626, 1350–1366.

Takano, S., Tanimizu, M., Hirata, T., Sohrin, Y., 2014. Isotopic constraints on

biogeochemical cycling of copper in the ocean. Nat. Commun. 5.

Takano, S., et al., 2017. A simple and rapid method for isotopic analysis of nickel,

copper, and zinc in seawater using chelating extraction and anion exchange. Anal.

Chim. Acta 967, 1–11.

Takano, S., et al., 2020. Sources of particulate Ni and Cu in the water column of the

northern South China Sea: evidence from elemental and isotope ratios in aerosols

and sinking particles. Mar. Chem. 219, 103751.

Takano, S., et al., 2021. Isotopic analysis of nickel, copper, and zinc in various freshwater

samples for source identification. Geochem. J. 55 (3), 171–183.

Thompson, C.M., Ellwood, M.J., 2014. Dissolved copper isotope biogeochemistry in the

Tasman Sea, SW Pacific Ocean. Mar. Chem. 165 (0), 1–9.

Twining, B.S., Baines, S.B., 2013. The trace metal composition of marine phytoplankton.

Annu. Rev. Mar. Sci. 5 (1), 191–215.

Vance, D., et al., 2016. The oceanic budgets of nickel and zinc isotopes: the importance of

sulfidic environments as illustrated by the Black Sea. Philos. Trans. R. Soc. A Math.

Phys. Eng. Sci. 374 (2081).

Vance, D., de Souza, G.F., Zhao, Y., Cullen, J.T., Lohan, M.C., 2019. The relationship

between zinc, its isotopes, and the major nutrients in the North-East Pacific. Earth

Planet. Sci. Lett. 525, 115748.

Ventura, G.T., et al., 2015. The stable isotope composition of vanadium, nickel, and

molybdenum in crude oils. Appl. Geochem. 59, 104–117.

Vu, H.T.D., Sohrin, Y., 2013. Diverse stoichiometry of dissolved trace metals in the

Indian Ocean. Sci. Rep. 3.

Wang, R.M., Archer, C., Bowie, A.R., Vance, D., 2019. Zinc and nickel isotopes in

seawater from the Indian Sector of the Southern Ocean: the impact of natural iron

fertilization versus Southern Ocean hydrography and biogeochemistry. Chem. Geol.

511, 452–464.

Wang, Q., et al., 2020. The geochemical behavior of Cu and its isotopes in the Yangtze

River. Sci. Total Environ. 728, 138428.

Weber, T., John, S., Tagliabue, A., DeVries, T., 2018. Biological uptake and reversible

scavenging of zinc in the global ocean. Science 361 (6397), 72–76.

Wen, Y., Yang, Z., Xia, X., 2013. Dissolved and particulate zinc and nickel in the Yangtze

River (China): distribution, sources and fluxes. Appl. Geochem. 31, 199–208.

Wu, S.-P., et al., 2019. Source apportionment of PM2.5 at urban and suburban sites in a

Port City of Southeastern China. Aerosol Air Qual. Res. 19 (9), 2017–2031.

Xie, X., Liu, X., Wang, H., Wang, Z., 2016. Effects of aerosols on radiative forcing and

climate over East Asia with different SO2 emissions. Atmosphere 7 (8), 99.

Yang, S.-C., et al., 2020. A new purification method for Ni and Cu stable isotopes in

seawater provides evidence for widespread Ni isotope fractionation by

phytoplankton in the North Pacific. Chem. Geol. 547, 119662.

Yang, S.-C., et al., 2021. Lack of redox cycling for nickel in the water column of the

Eastern tropical north pacific oxygen deficient zone: insight from dissolved and

particulate nickel isotopes. Geochim. Cosmochim. Acta 309, 235–250.

Yin, S., Feng, C., Li, Y., Yin, L., Shen, Z., 2015. Heavy metal pollution in the surface water

of the Yangtze estuary: a 5-year follow-up study. Chemosphere 138, 718–725.

Zhang, M., Sun, X., Xu, J., 2020a. Heavy metal pollution in the East China Sea: a review.

Mar. Pollut. Bull. 159, 111473.

Zhang, Z., et al., 2020b. Spatial variations of phytoplankton biomass controlled by river

plume dynamics over the lower Changjiang estuary and adjacent shelf based on

high-resolution observations. Front. Mar. Sci. 7 (906).

Zhao, Y., Vance, D., Abouchami, W., de Baar, H.J.W., 2014. Biogeochemical cycling of

zinc and its isotopes in the Southern Ocean. Geochim. Cosmochim. Acta 125 (0),

653–672.

Zheng, L., Minami, T., Takano, S., Ho, T.-Y., Sohrin, Y., 2021. Sectional distribution

patterns of Cd, Ni, Zn, and Cu in the North Pacific Ocean: relationships to nutrients

and importance of scavenging. Glob. Biogeochem. Cycles 35 (7) e2020GB006558.

Zhou, P., et al., 2018. Water mass analysis of the East China Sea and interannual

variation of Kuroshio subsurface water intrusion through an optimum

multiparameter method. J. Geophys. Res. Oceans 123 (5), 3723–3738.

John, S.G., 2007. The marine biogeochemistry of zinc isotopes. WHOI Theses.

John, S.G., Conway, T.M., 2014. A role for scavenging in the marine biogeochemical

cycling of zinc and zinc isotopes. Earth Planet. Sci. Lett. 394, 159–167.

John, S.G., Helgoe, J., Townsend, E., 2018. Biogeochemical cycling of Zn and Cd and

their stable isotopes in the Eastern Tropical South Pacific. Mar. Chem. 201, 256–262.

K¨

obberich, M., Vance, D., 2019. Zn isotope fractionation during uptake into marine

phytoplankton: implications for oceanic zinc isotopes. Chem. Geol. 523, 154–161.

Lemaitre, N., et al., 2020. Pervasive sources of isotopically light zinc in the North

Atlantic Ocean. Earth Planet. Sci. Lett. 539, 116216.

Liao, W.-H., Ho, T.-Y., 2018. Particulate trace metal composition and sources in the

Kuroshio adjacent to the East China Sea: the importance of aerosol deposition.

J. Geophys. Res. Oceans 123 (9), 6207–6223.

Liao, W.-H., et al., 2020. Zn isotope composition in the water column of the northwestern

Pacific Ocean: the importance of external sources. Glob. Biogeochem. Cycles 34 (1)

e2019GB006379.

Liao, W.-H., et al., 2021. Zn elemental and isotopic features in sinking particles of the

South China Sea: implications for its sources and sinks. Geochim. Cosmochim. Acta

314, 68–84.

Little, S.H., Vance, D., Walker-Brown, C., Landing, W.M., 2014. The oceanic mass

balance of copper and zinc isotopes, investigated by analysis of their inputs, and

outputs to ferromanganese oxide sediments. Geochim. Cosmochim. Acta 125 (0),

673–693.

Little, S.H., et al., 2018. Paired dissolved and particulate phase Cu isotope distributions

in the South Atlantic. Chem. Geol. 502, 29–43.

Little, S.H., et al., 2020. Towards balancing the oceanic Ni budget. Earth Planet. Sci. Lett.

547, 116461.

L´

opez, L., Lo M´

onaco, S., 2017. Vanadium, nickel and sulfur in crude oils and source

rocks and their relationship with biomarkers: implications for the origin of crude oils

in Venezuelan basins. Org. Geochem. 104, 53–68.

Middag, R., de Baar, H.J.W., Bruland, K.W., 2019. The relationships between dissolved

zinc and major nutrients phosphate and silicate along the GEOTRACES GA02

transect in the West Atlantic Ocean. Glob. Biogeochem. Cycles 33 (1), 63–84.

Middag, R., de Baar, H.J.W., Bruland, K.W., van Heuven, S.M.A.C., 2020. The

distribution of nickel in the West-Atlantic Ocean, its relationship with phosphate and

a comparison to cadmium and zinc. Front. Mar. Sci. 7 (105).

Morel, F.M.M., Price, N.M., 2003. The biogeochemical cycles of trace metals in the

oceans. Science 300 (5621), 944–947.

Nakaguchi, Y., et al., 2020. Distribution and stoichiometry of Al, Mn, Fe, Co, Ni, Cu, Zn,

Cd, and Pb in the East China Sea. J. Oceanogr. 77, 463–485.

Nakamura, H., et al., 2013. Intermediate and deep water formation in the Okinawa

trough. J. Geophys. Res. Oceans 118 (12), 6881–6893.

Ochoa-Gonzalez, R., et al., 2016. New insights from zinc and copper isotopic

compositions into the sources of atmospheric particulate matter from two major

European cities. Environ. Sci. Technol. 50 (18), 9816–9824.

Park, S., et al., 2019. Variability of aerosol optical properties observed at a polluted

marine (Gosan, Korea) and a High-Altitude Mountain (Lulin, Taiwan) site in the

Asian continental outflow. Aerosol Air Qual. Res. 19 (6), 1272–1283.

Peltier, R.E., Lippmann, M., 2009. Residual oil combustion: 2. Distributions of airborne

nickel and vanadium within New York City. J. Expos. Sci. Environ. Epidemiol. 20,

342.

Peltier, R.E., Hsu, S.-I., Lall, R., Lippmann, M., 2008. Residual oil combustion: a major

source of airborne nickel in New York City. J. Expos. Sci. Environ. Epidemiol. 19,

603.

Petit, J.C.J., et al., 2013. Anthropogenic sources and biogeochemical reactivity of

particulate and dissolved Cu isotopes in the turbidity gradient of the Garonne River

(France). Chem. Geol. 359 (0), 125–135.

Posacka, A.M., et al., 2017. Dissolved copper (dCu) biogeochemical cycling in the

subarctic Northeast Pacific and a call for improving methodologies. Mar. Chem. 196,

47–61.

Revels, B.N., Rickli, J., Moura, C.A.V., Vance, D., 2021. Nickel and its isotopes in the

Amazon Basin: the impact of the weathering regime and delivery to the oceans.

Geochim. Cosmochim. Acta 293, 344–364.

Roshan, S., Wu, J., 2015. The distribution of dissolved copper in the tropical-subtropical

North Atlantic across the GEOTRACES GA03 transect. Mar. Chem. 176, 189–198.

Ruacho, A., et al., 2020. Organic dissolved copper speciation across the U.S. GEOTRACES

equatorial Pacific zonal transect GP16. Mar. Chem. 225, 103841.

Samanta, M., Ellwood, M.J., Sinoir, M., Hassler, C.S., 2017. Dissolved zinc isotope

cycling in the Tasman Sea, SW Pacific Ocean. Mar. Chem. 192, 1–12.

11

...