For a century, the discovery of ferromanganese (Fe–Mn) nodules in the World Ocean was universally and indisputably credited to the Challenger circum-global oceanographic expedition of 1872–1876, during which the first manganese nodules and crusts were dredged up from the sea floor in February–March 1873. A century later, a counterclaim appeared in the literature, crediting Nordenskiöld’s expedition on Sofia in 1868, five years before the Challenger findings, for the discovery of Fe–Mn nodules in the ocean. This counterclaim, widely accepted without scrutiny, was based on the Gustaf Lindström (1884) chemical analysis of a single bottom sediment sample among 14 samples from two Arctic expeditions led by Nordenskiöld:Sofia 1868 and Vega 1878–1880. The Lindström (1884) report published as an eight-page brochure in Swedish remained almost unknown to the research community until now. A close examination of this report and other historical evidence revealed that the counterclaim of discovery by the Sofia 1868 expedition to the Kara Sea is invalid based on three notable facts: (1) Sofia never sailed in the Kara Sea; (2) the single bottom sediment sample with an extremely high content of Mn (24%), was collected in the Kara Sea during the Vega Expedition across the Northeast Passage; (3) the Vega sampling was in 1878, not in 1868. Meanwhile, five and a half years prior to the Vega sampling, the first Fe–Mn nodules and crusts were dredged up from the sea floor on 18 February and March 7, 1873 during the Challenger expedition. These findings have been promptly reported and published in May 1873. Thus, the credit for the discovery of ferromanganese nodules in the World Ocean firmly belongs to the Challenger expedition.

Tracing riverine freshwater transport pathways within the Arctic Ocean is key to understanding changes in Arctic Ocean freshwater inventories. Dissolved Ba concentrations have been used in this capacity but are compromised by non-conservative processes. To assess the potential for Ba isotopes to provide insights into the impact of such processes on Arctic Ocean dissolved Ba inventories, Ba concentration and isotope data for surface seawater samples from the Siberian Shelf and Bering Sea/Strait are presented. These samples capture the mixing of riverine freshwater discharged by the rivers Yenisey, Lena and Ob, with Atlantic and Pacific derived seawater, which are traced by relationships between salinity, Ba concentration and δ138/134Ba. The δ138/134Ba of net river inputs, following modification by estuarine processes, are constrained to be 0.31 ± 0.04‰, 0.20 ± 0.06‰ and 0.23 ± 0.04‰, for the rivers Yenisey, Lena and Ob respectively. These values are used to estimate an average δ138/134Ba for Eurasian river freshwater input to the Arctic Ocean of 0.23 ± 0.04‰. The Ba concentration and δ138/134Ba of Lena River freshwater transported across the Laptev Sea are modified by non-conservative processes. These non-conservative processes do not result in distinctive modification of dissolved Ba concentration-δ138/134Ba mixing relationships between Eurasian riverine freshwater and Arctic seawater, which unfortunately limits the potential of Ba isotopes to improve tracing riverine freshwater sources in the central Arctic Ocean basins using dissolved Ba inventories. More generally the results of this study help advance understanding of Ba isotope cycling in the environment and their development as an emerging tracer of marine processes.

Tracing riverine freshwater transport pathways within the Arctic Ocean is key to understanding changes in Arctic Ocean freshwater inventories. Dissolved Ba concentrations have been used in this capacity but are compromised by non-conservative processes. To assess the potential for Ba isotopes to provide insights into the impact of such processes on Arctic Ocean dissolved Ba inventories, Ba concentration and isotope data for surface seawater samples from the Siberian Shelf and Bering Sea/Strait are presented. These samples capture the mixing of riverine freshwater discharged by the rivers Yenisey, Lena and Ob, with Atlantic and Pacific derived seawater, which are traced by relationships between salinity, Ba concentration and δ138/134Ba. The δ138/134Ba of net river inputs, following modification by estuarine processes, are constrained to be 0.31 ± 0.04‰, 0.20 ± 0.06‰ and 0.23 ± 0.04‰, for the rivers Yenisey, Lena and Ob respectively. These values are used to estimate an average δ138/134Ba for Eurasian river freshwater input to the Arctic Ocean of 0.23 ± 0.04‰. The Ba concentration and δ138/134Ba of Lena River freshwater transported across the Laptev Sea are modified by non-conservative processes. These non-conservative processes do not result in distinctive modification of dissolved Ba concentration-δ138/134Ba mixing relationships between Eurasian riverine freshwater and Arctic seawater, which unfortunately limits the potential of Ba isotopes to improve tracing riverine freshwater sources in the central Arctic Ocean basins using dissolved Ba inventories. More generally the results of this study help advance understanding of Ba isotope cycling in the environment and their development as an emerging tracer of marine processes.

A major surface circulation feature of the Arctic Ocean is the Transpolar Drift (TPD), a current that transports river‐influenced shelf water from the Laptev and East Siberian Seas toward the center of the basin and Fram Strait. In 2015, the international GEOTRACES program included a high‐resolution pan‐Arctic survey of carbon, nutrients, and a suite of trace elements and isotopes (TEIs). The cruises bisected the TPD at two locations in the central basin, which were defined by maxima in meteoric water and dissolved organic carbon concentrations that spanned 600 km horizontally and ~25–50 m vertically. Dissolved TEIs such as Fe, Co, Ni, Cu, Hg, Nd, and Th, which are generally particle‐reactive but can be complexed by organic matter, were observed at concentrations much higher than expected for the openocean setting. Other trace element concentrations such as Al, V, Ga, and Pb were lower than expected due to scavenging over the productive East Siberian and Laptev shelf seas. Using a combination of radionuclide tracers and ice drift modeling, the transport rate for the core of the TPD was estimated at 0.9 ± 0.4 Sv(106m3 s−1). This rate was used to derive the mass flux for TEIs that were enriched in the TPD, revealing the importance of lateral transport in supplying materials beneath the ice to the central Arctic Ocean and potentially to the North Atlantic Ocean via Fram Strait. Continued intensification of the Arctic hydrologicc ycle and permafrost degradation will likely lead to an increase in the flux of TEIs into the Arctic Ocean.

Continental shelves and shelf seas play a central role in the global carbon cycle. However,

their importance with respect to trace element and isotope (TEI) inputs to ocean basins

is less well understood. Here, we present major findings on shelf TEI biogeochemistry

from the GEOTRACES programme as well as a proof of concept for a new method to

estimate shelf TEI fluxes. The case studies focus on advances in our understanding of TEI

cycling in the Arctic, transformations within a major river estuary (Amazon), shelf sediment

micronutrient fluxes and basin-scale estimates of submarine groundwater discharge. The

proposed shelf flux tracer is 228-radium (T1/2 =5.75 yr), which is continuously supplied to

the shelf from coastal aquifers, sediment porewater exchange and rivers. Model-derived shelf

228Ra fluxes are combined with TEI/ 228Ra ratios to quantify ocean TEI fluxes from the

western North Atlantic margin. The results from this new approach agree well with previous

estimates for shelf Co, Fe, Mn and Zn inputs and exceed published estimates of atmospheric

deposition by factors of approximately 3–23. Lastly, recommendations are made for additional

GEOTRACES process studies and coastal margin-focused section cruises that will help refine

the model and provide better insight on the mechanisms driving shelf-derived TEI fluxes

to the ocean.

This article is part of the themed issue ‘Biological and climatic impacts of ocean trace element

chemistry’.

The oxygenation of the atmosphere ∼2.45–2.32 billion years ago (Ga) is one of the most significant geological events to have affected Earth’s redox history. Our understanding of the timing and processes surrounding this key transition is largely dependent on the development of redox-sensitive proxies, many of which remain unexplored. Here we report a shift from negative to positive copper isotopic compositions (δ65CuERM-AE633) in organic carbon-rich shales spanning the period 2.66–2.08 Ga. We suggest that, before 2.3 Ga, a muted oxidative supply of weathering-derived copper enriched in 65Cu, along with the preferential removal of 65Cu by iron oxides, left seawater and marine biomass depleted in 65Cu but enriched in 63Cu. As banded iron formation deposition waned and continentally sourced Cu became more important, biomass sampled a dissolved Cu reservoir that was progressively less fractionated relative to the continental pool. This evolution toward heavy δ65Cu values coincides with a shift to negative sedimentary δ56Fe values and increased marine sulfate after the Great Oxidation Event (GOE), and is traceable through Phanerozoic shales to modern marine settings, where marine dissolved and sedimentary δ65Cu values are universally positive. Our finding of an important shift in sedimentary Cu isotope compositions across the GOE provides new insights into the Precambrian marine cycling of this critical micronutrient, and demonstrates the proxy potential for sedimentary Cu isotope compositions in the study of biogeochemical cycles and oceanic redox balance in the past.

Riverine Fe input is the primary Fe source to the ocean. This study is focused on the distribution of Fe along the Lena River freshwater plume in the Laptev Sea using samples from a 600 km long transect in front of the Lena River mouth. Separation of the particulate (>0.22µm), colloidal (0.22µm – 1kDa), and truly dissolved (<1kDa) fractions of Fe was carried out. The total Fe concentrations ranged from 0.15 to 57 µM with Fe dominantly as particulate Fe. The loss of > 99% of particulate Fe and about 90% of the colloidal Fe was observed across the shelf, while the truly dissolved phase was almost constant across the Laptev Sea. Thus, the truly dissolved Fe could be an important source of bioavailable Fe for plankton in the central Arctic Ocean, together with the colloidal Fe. Fe-isotope analysis showed that the particulate phase and the sediment below the Lena River freshwater plume had negative δ⁵⁶Fe values (relative to IRMM-14). The colloidal Fe phase showed negative δ⁵⁶Fe values close to the river mouth (about -0.20‰) and positive δ⁵⁶Fe values in the outermost stations (about +0.10‰).

We suggest that the shelf zone acts as a sink for Fe particles and colloids with negative δ⁵⁶Fe values, representing chemically reactive ferrihydrites. While the positive δ⁵⁶Fe values of the colloidal phase within the outer Lena River freshwater plume, might represent Fe-oxyhydroxides, which remain in the water column, and will be the predominant δ⁵⁶Fe composition in the Arctic Ocean.

The⁸⁷Sr/⁸⁶Sr isotope ratio has been widely used as aphysical tool to date and correlate carbonate successions due to the long Srresidence time in comparison with the ocean mixing time. If this method workson oceanic successions, marginal basins may show different Sr isotope recordsin comparison with the coeval ocean one due to sea-level variations,continental run-off and restricted water exchanges. In this work, we present the⁸⁷Sr/⁸⁶Sr isotope record of the upper Miocene carbonateramp of the Lithothamnion Limestone(Majella Mountain, central Apennines), as an example of the onset of restrictedwater exchanges between a marginal basin and the ocean water masses. The overalllatemost Tortonian–earlyMessinian Sr isotope record of the Lithothamnion Limestonefits below the global reference line. This deviation has been interpreted as dueto the strong control that freshwater input and enhanced continental run-off,linked to the migration of the Apennine accretionary wedge and foredeep system,have had on the central Adriatic water chemistry. These results imply that anaccurate oceanographic and geodynamic framework along with diagenetic overprintinvestigation has to be taken into consideration prior to apply SIS oncarbonate successions on marginal basins, even when facies analyses indicatefully marine conditions. This seems to be the case for the upper MioceneCentral Mediterranean carbonate successions, but may have more general validityand be extended to other recent or past marginal basins.

We here investigate the spatial and temporal variability of eolian dust particle sorting recorded in the Dome B (77 05 S, 94 55 E) ice core, central East Antarctica, during Marine Isotope Stage (MIS) 2. We address the question whether such changes reflect variable transport pathways from a unique source area or rather a variable apportionment from diverse Southern Hemisphere sources transported at different elevation in the troposphere. The Sr-Nd radiogenic isotope composition of glacial dust samples as well as single-particle Raman mineralogy support the hypothesis of a single dust provenance both for coarse and fine mode dust events at Dome B. The southern South American provenance of glacial dust in Antarctica deduced from these results indicate a dust composition coherent with a mixture of volcanic material and minerals derived from metamorphic and plutonic rocks. Additionally, Dome B glacial samples contain aragonite particles along with diatom valves of marine benthic/epiphytic species and freshwater species living today in the northern Antarctic Peninsula and southern South America. These data suggest contribution from the exposed Patagonian continental shelf and glacial outwash plains of southern Patagonia at the time when sea level reached its minimum. Our results confirm that dust sorting is controlled by the relative intensity of the two main patterns of tropospheric dust transport onto the inner Plateau, i.e. fast low-level advection and long-range high-altitude transport including air subsidence over Antarctica.

Strontium isotope analysis of skeletal material as a means to reconstruct prehistoric residential patterns has previously mainly been applied to populations with terrestrial diets. Here we present a model for populations with mixed marine/terrestrial diets, which is based on two-component mixing of strontium isotopes. Applying this model, we can estimate the original strontium isotope value of the terrestrial component of the diet. Accordingly it is possible to identify non-local individuals even if they had a mixed marine/terrestrial diet. The model is applied to tooth enamel samples representing nine individuals recovered from a passage grave in Resmo, on the island of Öland in the Baltic Sea, where at least five non-local individuals, representing at least two different geographical regions of origin, were identified. Non-local individuals were more frequent during the Bronze Age than during previous phases.

231Pa, 230Th and 232Th were analyzed in filtered seawater (n=70) and suspended particles (n=39) collected along a shelf-basin transect from the Barents shelf to the Makarov Basin in the Arctic Ocean during GEOTRACE Ssection GN04 in 2015. The distribution of dissolved 231Pa and 230Th in the Arctic Ocean deviates from the linear increase expected from reversible scavenging. Higher 232Th concentrations were observed at the shelf, slope and in surface waters in the deep basin, pointing at lithogenic sources. Fractionation factors (FTh/Pa) observed at the Nansen margin were higher compared to FTh/Pa in the central Nansen Basin, possibly due to the residual occurrence of hydrothermal particles in the deep central Nansen Basin. Application of a boundary scavenging model quantitatively accounts for the dissolved and particulate 230Th distributions in the Nansen Basin. Modelled dissolved 231Pa distributions were largely overestimated, which was attributed to the absence of incorporation of water exchange with the Atlantic Ocean in the model. 231Pa/230Th ratios of the suspended particles of the Nansen Basin were below the 231Pa/230Th production ratio, but top-core sediments of the Nansen margin and slope have high 231Pa/230Th-ratios, suggesting that scavenging along the Nansen margin partly actsas a sink for the missing Arctic 231Pa.

²³¹Pa, ²³⁰Th and ²³²Th were analyzed in unfiltered sea water samples (n = 66) and suspended particles (n = 19) collected in the Mediterranean Sea during the MedSeA-GA04-S cruise along the GEOTRACES section GA04S and used to investigate mechanisms controlling the distribution and fractionation of Pa and Th in an ocean margin environment. ²³¹Pa and²³⁰Th are particle reactive radionuclides and are often used astracers of processes such as boundary scavenging, particle transport and ocean circulation. The depth profiles of total ²³¹Pa and ²³⁰Th concentrations in the Mediterranean Sea displayed non-linear shapes. Higher total ²³²Th concentrations were observed at the straits and in deepwaters pointing at lithogenic sources. Fractionation factors F_Th/Pa ranged from 1.4 to 9. Application of a box-model illustrated that 94 % of the ²³¹Pa and almost all of the ²³⁰Th (99.9 %) produced in the Mediterranean Sea is removed to the sediment by scavenging. The negligible export of ²³⁰Th to the Atlantic Ocean, leads to a reevaluation of the mean settling speed of the filtered particles, which is now estimated to 500-1000 m/y. The low F_Th/Pa fractionation factors are attributed to the efficient scavenging and lack of transport of ²³¹Pa to the Atlantic Ocean.

The first inter-calibration study of the stable silicon isotope composition of dissolved silicic acid in seawater, d³⁰Si(OH)₄, is presented as a contribution to the international GEOTRACES program. Eleven laboratories from seven countries analyzed two seawater samples from the North Pacific subtropical gyre (Station ALOHA) collected at 300 m and at 1000 m water depth. Sampling depths were chosen to obtain samples with a relatively low (9 mmol L^-1, 300 m) and a relatively high (113 mmol L^-1, 1000 m) silicic acid concentration as sample preparation differs for low- and high concentration samples. Data for the 1000 m water sample were not normally distributed so the median is used to represent the central tendency for the two samples. Median d³⁰Si(OH)₄ values of +1.66‰ for the low-concentration sample and +1.25‰ for the high-concentration sample were obtained. Agreement among laboratories is overall considered very good; however, small but statistically significant differences among the mean isotope values obtained by different laboratories were detected, likely reflecting inter-laboratory differences in chemical preparation including preconcentration and purification methods together with different volumes of seawater analyzed, andthe use of different mass spectrometers including the Neptune MC-ICP-MS (Thermo Fisher™, Germany), the Nu Plasma MC-ICP-MS (Nu Instruments™, Wrexham, UK), and the Finnigan™ (now Thermo Fisher™, Germany) MAT 252 IRMS. Future studies analyzing d³⁰Si(OH)₄ in seawater should also analyze and report values for these same two reference waters in order to facilitate comparison of data generated among and within laboratories over time.

Rivers are significant contributors of Fe to theocean. However, the characteristics of chemically reactive Fe remain poorly constrained, especially in large Arctic rivers, which drain landscapes highly susceptible to climate change and carbon cycle alteration. The aim of this study was a detailed characterisation (size, mineralogy, and speciation) of riverine Fe-bearing particles (> 0.22 µm) and colloids (1 kDa – 0.22 µm) and their association with organic carbon (OC), in the Lena River and tributaries, which drain a catchment almost entirely underlain by permafrost. Samples fromthe main channel and tributaries representing watersheds that span a wide rangein topography and lithology were taken after the spring flood in June 2013 and summer baseflow in July 2012. Fe-bearing particles were identified, usingTransmission Electron Microscopy, as large (200 nm – 1 µm) aggregates of smaller (20 nm - 30 nm) spherical colloids of chemically-reactive ferrihydrite.In contrast, there were also large (500 nm – 1 µm) aggregates of clay (illite) particles and smaller (100 - 200 nm) iron oxide particles (dominantly hematite) that contain poorly reactive Fe. TEM imaging and Scanning Transmission X-raymicroscopy (STXM) indicated that the ferrihydrite is present as discrete particles within networks of amorphous particulate organic carbon (POC) and attached to the surface of primary produced organic matter and clay particles.Together, these larger particles act as the main carriers of nanoscale ferrihydrite in the Lena River basin.  The chemically reactive ferrihydrite accounts for on average 70 ± 15 % of the total suspended Fe in the Lena River and tributaries. These observations place important constraints on Fe and OC cycling in the Lena River catchment area and Fe-bearing particle transport to the Arctic Ocean.

Submarine groundwater discharge (SGD) to the Gulf of Bothnia, Baltic Sea, has been believed to be insignificant from hydrological models, yet geochemical investigations of SGD in this basin are limited. In this study, ²²³Ra, ²²⁴Ra, ²²⁶Ra, and ²²⁸Ra have been complemented by stable δ¹⁸O and d²H isotopes to characterize and quantify SGD rates from the coast of Forsmark, Sweden to Öregrundsgrepen Strait (Gulf of Bothnia). In shallow bays, SGD has been traced using relations between Ra, d²H and d¹⁸O isotopes and salinity. Zonal SGD from deformation zones, expressed as hydraulically conductive fractures, overlain by the Börstilåsen esker, a strip of conductive gravel sediment, have been traced through offshore ²²⁴Ra_xs and ²²⁶Ra trends. On the basis of a ²²⁴Ra_xs mass balance, the SGD flow rate ranges from (5.5 ± 3.0) · 10³ m³ d^-1 to (950 ± 520) · 10³ m³ d^-1. These rates are up to two orders of magnitude higher than those determined from local hydrological models, which consider only the fresh component of SGD. From the divergence between the hydrological and ²²⁴Ra_xs models, it is inferred that the site is influenced by a component of recirculated seawater.

223Ra, 224Ra, 226Ra, and 228Ra isotopes have been measured in groundwaters from depths ranging 50–900 m in fractured crystalline bedrock (Forsmark, Sweden) to understand the reason for elevated (up to 150 μg/L) aqueous uranium (Uaq) at 400–650 m depth. Ra isotope data is interpreted alongside previously reported 222Rn, 234U, and 238U data, as well as PHREEQC geochemical modelling and uranium mineralogy. A novel, [223Ra/226Ra]GW-based approach (where brackets and “GW” subscript refer to expression of an activity ratio measured from groundwater) to groundwater residence time estimation shows that elevated [Uaq] is most common in Holocene-age groundwaters of marine origin. Although these groundwaters are geochemically reducing, the [223Ra/228Ra]corr (where “corr” subscript refers to a correction applied to compare [223Ra/228Ra]GW to the more commonly reported [226Ra/228Ra]GW) suggest that they interact with U-rich pegmatites containing Proterozoic- and Palaeozoic-age Ca-U(VI)-silicate minerals, which are undersaturated in the present groundwaters. Local aqueous U(VI) can be stabilized in Ca2UO2CO30 complexes at pe-values as low as −4.5 but is susceptible to reduction after a modest decrease in pe-value, alkalinity, or Ca concentration. The [223Ra/228Ra]corr and [224Ra/228Ra]GW also suggest that U(VI)aq precipitates as UO2+X at the interface betwee nmarine and non-marine groundwaters. From these data, local [Uaq] is proposed to be governed by on-going water-rock interaction involving old U(VI)-minerals.

Global warming in permafrost areas is expected to change fluxes of riverine organic carbon (OC) 22 to the Arctic Ocean. Here OC concentrations, stable carbon isotope signatures (δ13C) and carbon-23 nitrogen ratios (C/N) are presented from 22 sampling stations in the Lena River and 40 of its 24 tributaries. Sampling was conducted during two expeditions: the first in July 2012 in the south 25 and southeastern region and the second in June 2013 in the northern region of the Lena basin. 26 The data showed significant spatial differences in concentrations and major sources of OC. Mean 27 sub-catchment slopes were correlated with OC concentrations, implying that mountainous areas 28 in general had lower concentrations than lowland areas. δ13C and C/N data from tributaries 29 originating in mountainous areas indicated that both dissolved and particulate OC (DOC and 30 POC) were mainly derived from soil organic matter (SOM). In contrast, tributaries originating in 31 lowland areas had larger contributions from fresh vegetation to DOC, while aquatically produced 32 OC was the major source of POC. We suggest that these differences in dominant sources 33 indicated differences in dominant flow pathways. Tributaries with larger influence of fresh 34 vegetation probably had surficial flow pathways, while tributaries with more SOM influence had 35 deeper water flow pathways. Thus, the future export of OC to the Arctic Ocean will likely be 36 controlled by changes in spatial patterns in hydroclimatology and the depth of the active layers 37 influencing the dominant water flow pathways in Arctic river basins.

Increasing global temperatures are causing widespread changes in the Arctic, including permafrost thawing and altered freshwater inputs and trace metal and carbon fluxes into the ocean and atmosphere. Changes in the permafrost active layer thickness can affect subsurface water flow paths and water-rock interaction times, and hence weathering processes. Riverine lithium isotope ratios (reported as δ⁷Li) are tracers of silicate weathering that are unaffected by biological uptake, redox, carbonate weathering and primary lithology. Here we use Li isotopes to examine silicate weathering processes in one of the largest Russian Arctic rivers: the Lena River in eastern Siberia. The Lena River watershed is a large multi-lithological catchment, underlain by continuous permafrost. An extensive dataset of dissolved Li isotopic compositions of waters from the Lena River main channel, two main tributaries (the Aldan and Viliui Rivers) and a range of smaller sub tributaries are presented from the post-spring flood/early-summer period at the onset of active layer development and enhanced water-rock interactions. The Lena River main channel (average δ⁷Lidiss ~19‰) has a slightly lower isotopic composition than the mean global average of 23‰ (Huh

et al., 1998a). The greatest range of [Li] and δ⁷Lidiss are observed in catchments draining the south facing slopes of the Verkhoyansk Mountain Range. South-facing slopes in high-latitude, permafrost dominated regions are typically characterised by increased summer insolation and higher daytime temperatures relative to other slope aspects. The increased solar radiation on south-facing catchments promotes repeated freeze-thaw cycles, and contributes to more rapid melting of snow cover, warmer soils, and increased active layer thaw depths. The greater variability in δ⁷Li and [Li] in the south-facing rivers likely reflect the greater infiltration of melt water and enhanced water rock interactions within the active layer. A similar magnitude of isotopic fractionation is observed between the low-lying regions of the Central Siberian Plateau (and catchments draining into the Viliui River), and catchments draining the Verkhoyansk Mountain Range into the Aldan River. This is in contrast to global rivers in non permafrost terrains that drain high elevations or areas of rapid uplift, where high degrees of physical erosion promote dissolution of freshly exposed primary rock typically yielding low δ⁷Lidiss, and low lying regions exhibit high riverine δ⁷Li values resulting from greater water-rock interaction and formation of secondary mineral that fractionates Li isotopes. Overall, the range of Li concentrations and δ⁷Lidiss observed within the Lena River catchment are comparable to global rivers located in temperate and tropical regions. This suggests that cryogenic weathering features specific to permafrost regions (such as the continual exposure of fresh primary minerals due to seasonal freeze-thaw cycles, frost shattering and salt weathering), and climate (temperature and runoff), are not a dominant control on δ⁷Li variations. Despite vastly different climatic and weathering regimes, the same range of riverine δ⁷Li values globally suggests that the same processes govern Li geochemistry – that is, the balance between primary silicate mineral dissolution and the formation (or exchange with) secondary minerals. This has implications for the use of δ⁷Li as a palaeo weathering tracer for interpreting changes in past weathering regimes.

Dolomites in Arctic Ocean sediments are widely attributed to erosion and transport of sediments from northern Canada and Greenland. Coarse-grained dolomite-rich ice-rafted debris is often linked to iceberg transport, but the origin of fine-grained dolomite is less well constrained. A presumed source is the Mackenzie River. In this article, we fingerprint the minerogenic and isotopic (Nd and Sr) composition of deglacial and Holocene fine-grained sediments (<38 μm) from the shallow Mackenzie Trough. Sediments from an 81.5-m borehole (MTW01) were analyzed. The borehole is composed of a progradational (deltaic), transitional (transgressive), and marine unit (<9.4 cal. ka BP). The average dolomite content (~7 percent) and ɛNd signals (−13.3) are surprisingly constant in the progradational and marine units. The isotopic signature is inherited from the Interior Platform, the major underlying bedrock region of the Mackenzie River mainstream. The transitional unit contains fluctuations in ɛNd (−11.0 and −14.6), reflecting enhanced input from the North American Cordillera and Canadian Shield that are not associated with elevated amounts of dolomite. Additional studies combining minerogenic and detrital ɛNd analyses from sites proximal to the paleo-icestreams draining the Canadian Arctic are required to ascertain the origin of dolomite enrichment in central Arctic Ocean sediments.

Submarine groundwater discharge (SGD) has been identified as an

important source of Sr to the ocean and the SGD-driven Sr flux to the

global ocean has been recently re-evaluated (Beck et al. 2013). However,

the uncertainty of this value is still high because of the uncertainties

related to the determination of SGD flow rates and the paucity of

87Sr/86Sr data in SGD end-members. As carbonates have high Sr

concentrations and are subjected to intense heightened weathering, they

might significantly influence the SGD input of Sr to the ocean. Here we

present data on Sr concentrations and 87Sr/86Sr ratios in three carbonate

dominated sites of the western area of the Mediterranean Sea, a semienclosed

basin characterized by abundant coastal carbonates. The

87Sr/86Sr ratios in groundwater were lower compared to modern seawater (~

0.70916), as expected for areas dominated by carbonate lithologies.

Concentrations of Sr and 87Sr/86Sr ratios in groundwater showed

conservative mixing in the studied subterranean estuaries. By using SGD

flow rates reported in the literature for the study areas, a meteoric

SGD-driven Sr flux of (0.12 - 2.1)·103 mol d-1 km-1 was calculated for

the region, with a fresh SGD end-member characterized by a Sr

concentration of 27 - 30 μM and a 87Sr/86Sr ratio of 0.708020 - 0.707834.

Integrating these Sr data with literature data (i.e. values of Sr

concentration and 87Sr/86Sr ratio from other lithologies as well as SGD

flow rates), we also calculated the fresh SGD-driven Sr flux to the

entire Mediterranean Sea, obtaining a value of (0.34 - 0.83)·109 mol y-1,

with a 87Sr/86Sr of 0.7086 - 0.7081. Thus, for the entire Mediterranean

basin, SGD is globally a source of Sr less radiogenic compared to

seawater. The SGD Sr flux to the Mediterranean Sea represents 5-6% of the

SGD Sr flux to the global ocean and the Mediterranean SGD end-member has

higher Sr concentration (5.0 - 12 μM) than the global SGD end-member (2.9

μM). This confirms the significant role of carbonate lithologies on SGDdriven

Sr fluxes to seawater.

The fresh SGD-driven Sr flux to the Mediterranean Sea is about 20 - 50%

of the riverine Sr input and significantly higher than the input through

atmospheric dust deposition. Therefore SGD should be considered as an

important continental source of Sr to the basin.

Summer iron (Fe) fertilization in the Ross Sea has previously been observed in association with diatom productivity, lithogenic particles and excess Fe in the water column. This productivity event occurred during an early breakout of sea ice via katabatic winds, suggesting that aeolian dust could be an important source of lithogenic Fe required for diatom growth in the Ross Sea. Here we investigate the provenance of size-selected dust deposited on sea ice in McMurdo Sound, south-western (SW) Ross Sea. The isotopic signature of McMurdo Sound dust (0.70533< 87Sr/86Sr< 0.70915 and -1.1 < εNd(0) <3.45)confirms that dust is locally sourced from the McMurdo Sound debris bands and comprises a two-component mixture of McMurdo Volcanic Group and southern Victoria Land lithologies. In addition, the provenance of lithogenic sediment trapped in the water column was investigated, and the isotopic signature (εNd(0) =3.9, 87Sr/86Sr = 0.70434) is differentiated from long-range transported dust originating from South America and Australia. Elevated lithogenic accumulation rates in deeper sediment traps in the Ross Sea suggest that sinking articles in the water column cannot simply result from dust input at the surface. This discrepancy can be best explained by significant upwelling and remobilization of lithogenic Fe from the sea floor.

The Ross Sea, Antarctica, is a highly productive region of the Southern Ocean. Significant new sources of iron (Fe) are required to sustain phytoplankton blooms in the austral summer. Atmospheric deposition is one potential source. The fractional solubility of Fe is an important variable determining Fe availability for biological uptake. To constrain aerosol Fe inputs to the Ross Sea region, fractional solubility of Fe was analyzed in a snow pit from Roosevelt Island, eastern Ross Sea. In addition, aluminum, dust, and refractory black carbon (rBC) concentrations were analyzed, to determine the contribution of mineral dust and combustion sources to the supply of aerosol Fe. We estimate exceptionally high dissolved Fe (dFe) flux of 1.2 × 10⁻⁶ g m⁻² y⁻¹ and total dissolvable Fe flux of 140 × 10⁻⁶ g m⁻² y⁻¹ for 2011/2012. Deposition of dust, Fe, Al, and rBC occurs primarily during spring-summer. The observed background fractional Fe solubility of ~0.7% is consistent with a mineral dust source. Radiogenic isotopic ratios and particle size distribution of dust indicates that the site is influenced by local and remote sources. In 2011/2012 summer, relatively high dFe concentrations paralleled both mineral dust and rBC deposition. Around half of the annual aerosol Fe deposition occurred in the austral summer phytoplankton growth season; however, the fractional Fe solubility was low. Our results suggest that the seasonality of dFe deposition can vary and should be considered on longer glacial-interglacial timescales.

The Kalix River shows distinct temporal variations in the Sr-isotope ratio in filtered water (0.726 to 0.732). During base flow in winter the ⁸⁷Sr/⁸⁶Sr ratio is on average 0.730. When discharge increases and peaks during spring flood the ⁸⁷Sr/⁸⁶Sr ratio shows the most radiogenic (0.732) values. The temporal variations in the ⁸⁷Sr/⁸⁶Sr ratio in the Kalix River can be explained by mixing of water from the woodlands and the mountain areas.

During high water discharge in May the ⁸⁷Sr/⁸⁶Sr ratios are more radiogenic in the suspended phase (1 kDa - 70 µm) compared to the truly dissolved phase (<1 kDa). The difference in ⁸⁷Sr/⁸⁶Sr ratio between the two phases (Δ ⁸⁷Sr/⁸⁶Sr) is linearly correlated with the suspended iron concentration. During spring flood Sr and Fe derived from an additional source, reach the river. Deep groundwater has a more radiogenic ⁸⁷Sr/⁸⁶Sr isotope ratio than the Kalix River during spring flood and thus, represents a possible source for the suspended Fe and the associated Sr. Strontium can be coprecipitated with and adsorbed to different types of Fe aggregates. We propose that the Sr-isotope ratio in the suspended phase reflects the isotopic composition of the water at the interface between anoxic groundwater and oxic stream water in the riparian zone, where the Fe aggregates are formed. These particles dominate the suspended phase in the river and the mixing with mountain waters, poor in Fe, produces the difference in the isotopic signature. The different signatures in suspended and truly dissolved fraction indicate that these aggregates are relatively stable during stream-river transport. As such the ⁸⁷Sr/⁸⁶Sr can be used to trace the origin of the non-detrital suspended phase.