TY - JOUR

T1 - Correlated molybdenum and uranium isotope signatures in modern anoxic sediments

T2 - Implications for their use as paleo-redox proxy

AU - Brüske, Annika

AU - Weyer, Stefan

AU - Zhao, M. Y.

AU - Planavsky, N. J.

AU - Wegwerth, A.

AU - Neubert, N.

AU - Dellwig, O.

AU - Lau, K. V.

AU - Lyons, T. W.

N1 - Funding Information: We are thankful to Carolina Montoya-Pino, Vivien Schulte and Dorian Zok from LUH for assistance with isotope and trace metal analyses. Leopold Sauheitl is thanked for support with TOC measurements at LUH. Anne Köhler and Lisa Sieg are thanked for help with ICP-OES/-MS and Ines Scherff for TOC support at IOW. We thank the Captains and crews during cruises R/V Knorr, M72/5 and MSM33 in the Black Sea and specifically the cruise leaders Christian Borowski (M72/5) and Helge W. Arz (MSM33) of RVs Meteor and Maria S. Merian for support during sampling. We are thankful to Larry Peterson and the captains and crews of the PLUME07 cruise of the R/V Thomas Washington and the ODP leg 165 cruise in the Cariaco Basin. Funding for SW and AB was provided by program SPP1833 of the Deutsche Forschungsgemeinschaft (to SW grant WE2850-15/1). NJP acknowledges support from the NASA Alternative Earths Astrobiology Institute (under Cooperative Agreement No. NNA15BB03A issued through the Science Mission Directorate) and Packard foundation. TWL and KVL acknowledge funding from the Petroleum Research Fund of the American Chemical Society. We thank Morten Andersen and two anonymous reviewers for very constructive and helpful comments and Claudine Stirling for editorial handling.

PY - 2020/2/1

Y1 - 2020/2/1

N2 - Redox-sensitive trace metals and their isotopes have emerged as important tools that are used to reconstruct the redox-evolution of the ocean-atmosphere system. However, reliability of such reconstructions ultimately depends on a solid understanding of the proxies in the present-day oceanic system and their archival potential in sediments. This study compares isotope fractionation of molybdenum (Mo) and uranium (U) during their removal from seawater and deposition into sediments by investigating sites at various depths of the presently two largest restricted anoxic oceanic basins: The Black Sea and the Cariaco Basin. In support of previous investigations, our data indicate that Mo scavenging and isotope fractionation are mainly controlled by water column sulfide levels. In contrast to Mo, U reduction and immobilization appears to occur mainly at the sediment-water interface and within the uppermost few cm of the sediment pile in both basins. In the Black Sea, decreasing δ238U of surface sediments with increasing water depth correlate with trends for water column δ238U, implying constant U isotope fractionation between water and sediment. However, increasing U concentrations and δ238U within the uppermost few cm of the sediment pile of both basins indicate additional U reduction with depth. Despite the different mechanisms for Mo and U removal and associated isotope fractionations, a similar inverse correlation between δ98Mo and δ238U is observed for sediments of both basins, which translates in a positive correlation of Mo and U isotope fractionation between the sediments and open seawater. The correlation of δ98Mo and δ238U indicates a similar response of isotope fractionation to the efficiency of Mo and U removal that is mainly controlled by sulfate reduction rates. High dissolved sulfide concentrations and sulfate reduction rates are responsible for very effective Mo and U removal and corresponding minor Mo and U isotope fractionation relative to seawater. Further, high dissolved sulfide concentrations also correlate positively with deep water renewal times, resulting in an isotopically fractionated water column with low δ238U (and somewhat higher δ98Mo) in restricted basins with sluggish ventilations, such as the Black Sea. Both mechanisms result in negatively correlated δ98Mo and δ238U with high δ98Mo and low δ238U in sediments under strong euxinic conditions. The particularly strong correlation observed for Cariaco Basin sediments may indicate that its water column was variably stratified in the past. The observed δ98Mo and δ238U correlation of both basins can be reproduced in a simple coupled water column and sediment reactive transport model. Different slopes in δ98Mo and δ238U trends can be linked to varying degree of basin restriction, sulfate reduction rates, and isotope compositions of the respective water columns. The offset towards lower δ98Mo (and δ238U), observed for Cariaco Basin sediments compared to those from the Black Sea, may be the result of inefficient Mo reduction with high Mo isotope fractionation or isotopically light Mo from a particulate Fe-Mn oxide shuttle. The results of this study will help to interpret sedimentary Mo and U isotope values, while showing that coupling of δ98Mo and δ238U in sedimentary archives may be useful for paleo-reconstruction work.

AB - Redox-sensitive trace metals and their isotopes have emerged as important tools that are used to reconstruct the redox-evolution of the ocean-atmosphere system. However, reliability of such reconstructions ultimately depends on a solid understanding of the proxies in the present-day oceanic system and their archival potential in sediments. This study compares isotope fractionation of molybdenum (Mo) and uranium (U) during their removal from seawater and deposition into sediments by investigating sites at various depths of the presently two largest restricted anoxic oceanic basins: The Black Sea and the Cariaco Basin. In support of previous investigations, our data indicate that Mo scavenging and isotope fractionation are mainly controlled by water column sulfide levels. In contrast to Mo, U reduction and immobilization appears to occur mainly at the sediment-water interface and within the uppermost few cm of the sediment pile in both basins. In the Black Sea, decreasing δ238U of surface sediments with increasing water depth correlate with trends for water column δ238U, implying constant U isotope fractionation between water and sediment. However, increasing U concentrations and δ238U within the uppermost few cm of the sediment pile of both basins indicate additional U reduction with depth. Despite the different mechanisms for Mo and U removal and associated isotope fractionations, a similar inverse correlation between δ98Mo and δ238U is observed for sediments of both basins, which translates in a positive correlation of Mo and U isotope fractionation between the sediments and open seawater. The correlation of δ98Mo and δ238U indicates a similar response of isotope fractionation to the efficiency of Mo and U removal that is mainly controlled by sulfate reduction rates. High dissolved sulfide concentrations and sulfate reduction rates are responsible for very effective Mo and U removal and corresponding minor Mo and U isotope fractionation relative to seawater. Further, high dissolved sulfide concentrations also correlate positively with deep water renewal times, resulting in an isotopically fractionated water column with low δ238U (and somewhat higher δ98Mo) in restricted basins with sluggish ventilations, such as the Black Sea. Both mechanisms result in negatively correlated δ98Mo and δ238U with high δ98Mo and low δ238U in sediments under strong euxinic conditions. The particularly strong correlation observed for Cariaco Basin sediments may indicate that its water column was variably stratified in the past. The observed δ98Mo and δ238U correlation of both basins can be reproduced in a simple coupled water column and sediment reactive transport model. Different slopes in δ98Mo and δ238U trends can be linked to varying degree of basin restriction, sulfate reduction rates, and isotope compositions of the respective water columns. The offset towards lower δ98Mo (and δ238U), observed for Cariaco Basin sediments compared to those from the Black Sea, may be the result of inefficient Mo reduction with high Mo isotope fractionation or isotopically light Mo from a particulate Fe-Mn oxide shuttle. The results of this study will help to interpret sedimentary Mo and U isotope values, while showing that coupling of δ98Mo and δ238U in sedimentary archives may be useful for paleo-reconstruction work.

KW - Anoxic basin

KW - Black Sea

KW - Cariaco Basin

KW - Mo isotopes

KW - Paleo-redox proxy

KW - Reactive transport model

KW - U isotopes

UR - http://www.scopus.com/inward/record.url?scp=85077123009&partnerID=8YFLogxK

U2 - 10.1016/j.gca.2019.11.031

DO - 10.1016/j.gca.2019.11.031

M3 - Article

AN - SCOPUS:85077123009

VL - 270

SP - 449

EP - 474

JO - Geochimica et cosmochimica acta

JF - Geochimica et cosmochimica acta

SN - 0016-7037

ER -