Water Mass Tracer Research Articles

Rare earth elements and yttrium (REY) in fjord waters: Comparison between seawater in the Trondheimfjord (Norway), its local riverine REY sources and the North Atlantic

The rare earth elements and yttrium (REY) are critical resources increasingly released into the environment due to their pivotal role for an ever-growing number of high-tech products and processes. Fjords, worldwide and particularly in Norway, are not only of high importance for biodiversity but they also have great economic value. Knowledge on the distribution of REY in Norwegian coastal and riverine waters is, however, surprisingly scarce. We here report REY data for water samples from depth profiles from ten stations in the Trondheimfjord, one of Norway’s largest fjords, several Norwegian rivers, and two wastewater treatment plants in Trondheim.Our results show that water from different locations in the Trondheimfjord yield similar REY concentrations that correlate well with dissolved organic carbon. The deepest sample at each station shows the lowest REY concentrations. The shale-normalised (SN) REY patterns of the fjord waters resemble those of North Atlantic seawater, but can be distinguished from open-ocean water by the smaller fractionation between light and middle REY (PrSN/TbSN ≥ 0.5). Stations in the vicinity of a river mouth show considerably higher REY concentrations at shallow depths. The respective REYSN patterns resemble the typically flat patterns of boreal rivers that are often rich in nanoparticles and colloids (NPCs). The REYSN patterns of the four rivers investigated (Nidelva, Orkla, Gaula, Stjørdalselva) show the features of the shallow(er) fjord water samples but have even higher REY concentrations. Ultrafiltration (< 1 kDa) data for the Nidelva corroborate that the typical “REYSN seawater signature” is in fact already present in freshwater where it is, however, usually hidden by the REY associated with NPCs. The local wastewater treatment plants release anthropogenic Gd (from contrast agents used in magnetic resonance imaging) into the Trondheimfjord, but this signal is immediately diluted and thus is not observed in the REYSN patterns of the fjord water. However, our results in general suggest that the slightly elevated Gd/Tb ratios observed in almost all fjord waters relative to North Atlantic marine water may rather be due to the presence of anthropogenic Gd in the southern North Sea and the Baltic Sea, corroborating that anthropogenic Gd can be applied as a sensitive far-field watermass tracer.

Controls on Dissolved Barium and Radium‐226 Distributions in the Pacific Ocean Along GEOTRACES GP15

AbstractRadium‐226(226Ra) and barium (Ba) exhibit similar chemical behaviors and distributions in the marine environment, serving as valuable tracers of water masses, ocean mixing, and productivity. Despite their similar distributions, these elements originate from distinct sources and undergo disparate biogeochemical cycles, which might complicate the use of these tracers. In this study, we investigate these processes by analyzing a full‐depth ocean section of 226Ra activities (T1/2 = 1,600 years) and barium concentrations obtained from samples collected along the US GEOTRACES GP15 Pacific Meridional Transect during September–November 2018, spanning from Alaska to Tahiti. We find that surface waters possess low levels of 226Ra and Ba due to export of sinking particulates, surpassing inputs from the continental margins. In contrast, deep waters have higher 226Ra activities and Ba concentrations due to inputs from particle regeneration and sedimentary sources, with 226Ra inputs primarily resulting from the decay of 230Th in sediments. Further, dissolved 226Ra and Ba exhibit a strong correlation along the GP15 section. To elucidate the drivers of the correlation, we used a water mass analysis, enabling us to quantify the influence of water mass mixing relative to non‐conservative processes. While a significant fraction of each element's distribution can be explained by conservative mixing, a considerable fraction cannot. The balance is driven using non‐conservative processes, such as sedimentary, rivers, or hydrothermal inputs, uptake and export by particles, and particle remineralization. Our study demonstrates the utility of 226Ra and Ba as valuable biogeochemical tracers for understanding ocean processes, while shedding light on conservative and myriad non‐conservative processes that shape their respective distributions.

Suspended particulate matter influence on dissolved Nd concentration and isotopic composition along GEOTRACES section GP16

The role of suspended particulate matter in the biogeochemical cycling of neodymium (Nd) in the ocean is not well understood. This study reports the measurement of dissolved Nd concentrations and isotopes (<0.2 um), and particulate Nd concentrations along the Eastern Pacific Zonal Transect (EPZT, GP16) as part of the GEOTRACES program. The western part of the EPZT cruise track is influenced by a hydrothermal plume, observed between 2200 and 2800 m, originating at the southern East Pacific Rise. This setting allows for the investigation of the role of particulate matter in Nd biogeochemical cycling and its contribution in modifying the distribution of dissolved Nd. Results show that the highest removal of dissolved Nd (∼ 21 %) was observed near the hydrothermal ridge crest, decreasing to ∼ 8 % at the westernmost station. Here, we report the partition coefficient (Kd) of each particle constituent (e.g., lithics, CaCO3, POM, Opal, Fe-phase, Mn-phase) to show that particle composition plays an important role in Nd removal alongside particle mass. Along the plume, both particulate Mn and Fe contributed to the removal of Nd, with Mn playing the dominant role in sites closest to the vent. At the western stations, below the plume, the concentration of both dissolved and particulate Nd increased with depth, with particulate Nd one to two orders of magnitude lower than measured in the dissolved phase. The increase in dissolved Nd with depth in the interval below the plume could result either from the continuing remineralization of raining particles or the influx of dissolved Nd from bottom sediments. Close to the ridge crest, where the hydrothermal Nd input is at its highest, there is a hint of local modification of dissolved εNd signature, however not large enough to affect the use of εNd as a water mass tracer.

Trace elements in coralline algae as a new proxy for seawater chemistry and metal pollution

The abundances of some macronutrients, and trace elements (K, Al, P, V, Mn, Co, Ni, Cu, Zn, Rb, Sr, Mo, Cs, Ba, Pb, Th, U, Y and REE) were determined in a series of coralline algae (Lithothamnion corallioides) samples (n = 101) collected alive in the Bay of Brest and the Iroise Sea (Western Brittany, NW France), in order to assess the potential of these algae as archives of seawater chemistry and potential metal pollution. REE and Y (REY) patterns are similar in shape to those of local seawater, exhibiting similar La, Ce and Y anomalies, but with abundances ranging between 4 and 5 orders of magnitude higher than seawater values. Variations in La anomalies (La/La* = 1.29–2.08), Y anomalies (Y/Ho = 38.6–55.8), and heavy rare earth enrichments (Prsn/Ersn = 0.22–0.52) are consistent with mixing of seawater with rivers flowing into the Bay of Brest. The behavior of other trace elements, such as Al and Cs, also reflects this mixing. Other parameters and processes can control the abundances of the other elements measured. For example, the presence of organic matter in studied samples controls the abundances of K and Rb. The abundances of base metals (e.g., Co, Ni, Cu) are highly sensitive to the various pollutants present in the Bay of Brest. In particular, the Pb content of coralline algae clearly reflects the pollution caused by mining of a nearby Pb deposit from the 18th to the early 20th century. Our results demonstrate the potential of coralline algae not only for tracing water masses, but also for studying metal pollution.

Fjords Are Potential Hotspots of Refractory Dissolved Organic Matter Production: Insights From 1 Year of Weekly Time‐Series Observations of Fluorescent Dissolved Organic Matter in the Bedford Basin, a Northwestern Atlantic Fjord

AbstractFjords are representative marine ecosystems that play an important role in regulating coastal carbon cycling. As fingerprints of the dissolved organic matter (DOM) pool, fluorescent DOM (FDOM) is widely used to study the ocean carbon cycle. Here, we report on 1‐year of weekly observations of FDOM (from May 2018 to May 2019) in the Bedford Basin, a well‐studied northwestern Atlantic fjord. Results showed that differences in FDOM indices (biological index, fluorescence index, and humification indices) between the euphotic and aphotic layers changed during the investigation period, suggesting that classical definitions of these indices may not apply consistently. Spearman rank correlations showed that the surface FDOM was affected by physical and biological factors, while water mass renewal was the major control for the deeper layer. Humic‐like FDOM (FDOMH) changed following the Atlantic deep‐water intrusion, indicating that FDOMH may be used to trace water mass movements in this region. FDOMH shows a significantly positive linear correlation with apparent oxygen utilization (AOU). Their slopes were higher than those from the open ocean, suggesting that the Bedford Basin is a hotspot of RDOM production. Hence, we proposed a possible carbon sequestration mechanism that fjords play as “RDOM producing hot spots” and that the produced RDOM is then transported to the open ocean via water mass movement and finally stored in the ocean for extended periods of time. The proposed biogeochemical processes may also occur, more generally, in the global coastal ocean.

δ13C and δ15N zooplankton isoscapes as trace of water masses and mesoscale activity in the Pacific Tropical-Subtropical Convergence off Mexico during June 2010

This research analyzes for the first time in the Pacific Tropical-Subtropical Convergence off Mexico during June 2010 the relationships among the δ13C and δ15N signal distribution in the bulk zooplankton, water masses, and mesoscale structures. The environmental analysis showed that the California Current Water (CCW) and Transitional Water (TrW) converge where the 22 °C isotherm and 34.6 g kg−1 isohaline were observed (22°N). Two cyclonic eddies were detected: one in CCW at 24°N about 70 km in diameter, the other one located in TrW at 21°N with 150 km in diameter. A cluster analysis defined three zooplankton isoscapes with significant differences. Isoscape 1, immerses in CCW – the lowest δ13C (−22.37 ± 0.89 ‰) and δ15N (9.89 ± 1.32 ‰) – showed temperature (19.86 ± 1.97 °C), salinity (34.08 ± 0.37 g kg−1) values, the deepest thermocline (77.93 ± 25.51 m) and oxygen minimum zone (164.78 ± 44.96 m). The CCW was relatively oligotrophic without important mesoscale features in the sampled time within the sampled area. Isoscape 2, a cyclonic eddy in CCW – relatively enriched zooplankton δ13C values (−16.78 ± 1.95 ‰) due to the entry of enriched coastal biota– reflected in high chlorophyll a and subsequently assimilated into zooplankton tissues. Isoscape 3, a cyclonic eddy immerses in TrW – the highest δ15N (13.14 ± 1.60 ‰), salinity (34.76 ± 0.19 g kg−1) and temperature (19.90 ± 2.27 °C) values and shallowest thermocline (32.27 ± 18.63 m), and oxygen minimum zone (66.82 ± 37.68 m) in depth. Likely, this 15N-enriched recycled nitrate was pumped from the deoxygenated subsurface to the surface, reflected in the zooplankton bulks. The results showed that the isotopic signals in bulk zooplankton may be a good water mass and mesoscale activity tracer.

Terrigenous dissolved organic matter input and nutrient-light-limited conditions on the winter microbial food web of the Beagle Channel

The viral shunt and microbial loop are trophic pathways in the microbial food web, recognized as major drivers of carbon and nutrient cycles in the sea. The Beagle Channel, located at the southernmost extreme of South America, is a subantarctic marine environment influenced by terrestrial runoff and glacial meltwater with high temporal and spatial variability. There is a knowledge gap on the trophic pathways and the microbial food web in the eastern part of the Channel. We herein present for the first time a comprehensive and spatially wide study of the effects of physicochemical and bio-optical parameters on the microbial food web along the Eastern Beagle Channel. The study took place under winter hydrographic conditions, featuring weak vertical stratification of the water column and low chlorophyll a concentrations (0.13 ± 0.07 mg m−3). Biogeochemical gradients were notable between the inner and outer (easternmost) sectors of the Channel, separated by a shallow sill at Mackinlay Strait. As a chemical water mass tracer, the presence of the highest concentrations in bottom waters of NO3 + NO2 in the inner channel and the difference in the T-S diagram indicate the Subantarctic Pacific origin of this water mass. Structural equation models showed that the specific UV absorbance of water (SUVA254, a proxy for the aromatic carbon content) and NO3 + NO2 were the main parameters affecting the microbial food web in surface/subsurface waters suggesting that prokaryotes biomass was partially supported by allochthonous dissolved organic matter (DOM) derived from river discharges. Our results show a major role of the viral shunt in surface/subsurface waters retaining nutrients in the basal levels of the food web. We suggest that the viral shunt in surface/subsurface waters and the water residence time west of Mackinlay Strait allows infected cells and viral lysis products to reach bottom waters propelling the production of recalcitrant and labile DOM there.

Kinetic reactive transport explains distinct subsurface deposition patterns of pollutants in sediments. The case of the Sellafield-derived 236U, 137Cs and 239,240Pu in the Esk Estuary, UK

The kinetics of the uptake of pollutants by solids in sediments interacts with transitional eddy diffusivity in the pore fluid, leading to different depth-distribution patterns. This work aims to gain insights into the still poorly understood behaviour in the marine environment of the anthropogenic 236U, a recently postulated tracer of water masses. It is hypothesized that the transition from mobile U(VI) to highly particle-reactive U(IV) in the anoxic zone of the sediment produces a subsurface deposition pattern. A novel numerical model for kinetic reactive transport in sediments, which merges diagenetic processes for transport and box models for the uptake, is used for concept demonstration. It is applied to synthetic environments with high eddy diffusivity to obtain the singular depth-distribution patterns of pulsed inputs of tracers that mimic the anthropogenic 239,240Pu, 137Cs, and 236U. While the first is retained in the upper cm, the second shows an exponential penetration pattern over few cm, and 236U is deposited with a Gaussian-like pattern centred below the transition to the anoxic zone. These patterns are then merged into a diagenetic model to compute the depth distribution at decadal or centennial scales of dissolved and particle-bound inputs of these radiotracers. It is successfully applied to a real case using literature data for a sediment core from the Esk Estuary, UK, affected by radioactive releases from the Sellafield nuclear reprocessing plant. This work provides insight into until now poorly understood field data and provides a novel view of broad implications in the study of the behaviour of pollutants in surficial aquatic sediments.

Assessing neodymium isotopes as an ocean circulation tracer in the Southwest Atlantic

The global overturning ocean circulation plays a key role in global climate by distributing heat around the Earth and by triggering or amplifying major climate changes. Neodymium (Nd) isotopes are widely used to trace present-day and past ocean circulation changes; however, their value as a circulation tracer has been increasingly challenged by studies that have focused on processes that can modify seawater Nd isotope ratios (for example, seawater interaction with particles, pore water fluxes from sediments). The Southwest Atlantic represents an excellent test bed for investigating the integrity of Nd isotopes as an ocean circulation tracer, as it includes the major Atlantic northern and southern hemisphere-sourced end-member water masses associated with the global overturning ocean circulation, Antarctic Intermediate Water, North Atlantic Deep Water, and Antarctic Bottom Water (AAIW, NADW, and AABW, respectively) and potential regional sources of Nd that could impact that integrity. This study reports Nd isotope data on the GEOTRACES GA02 Southwest Atlantic Meridional Transect, spanning the equator to ∼50°S. Below the pycnocline, substantial non-conservative behavior is observed only in samples dominated by AAIW in the northern portion of the transect (∼25°S to the equator); this appears to reflect addition of Nd from the cratons of South America or Africa from above the pycnocline. This effect is not observed at depths directly below dominated by NADW. Otherwise, Nd isotopes behave as a near-conservative water mass tracer along the transect, with 48% of samples within analytical error of the predicted value from water mass mixing, and 84% within 0.9 εNd-units (∼3 times the analytical error), thus confirming its potential at most depths and locations in the Southwest Atlantic to reconstruct past ocean circulation changes.

Geochemical mobility of 137Cs in marine environments based on laboratory and field studies

Cesium-137, a unique geochemical tracer, behaves as a particle-reactive species in freshwater that is useful as a geochronometer, and soluble in seawater that is used as a water mass tracer, as evidenced by higher solid-solution partition coefficient, Kd, in freshwater and much lower Kd values in seawater. A suite of sediment cores were collected from the Southern Yellow Sea and coastal regions of Croatia in 2014 and analyzed for vertical profiles of excess 210Pb (210Pbex), 239+240Pu, and 137Cs. A set of laboratory experiments were also conducted to investigate the partitioning of 137Cs between a suite of solid material comprised of commonly occurring minerals in the environment and solution under different contact times, pH, and salinity. The partition coefficient showed that for illite Kd sharply increased during the first two hours and then slowly increased after 4 h. Overall, the salinity significantly affects the 137Cs behavior in aqueous environments. The Kd values of 137Cs were higher (6.5 × 103–1.1 × 104 mL g−1) when the salinity was below 0.5 psu but drastically decreased to 9.0 × 102 mL g−1 when salinity was 3.6 psu and then slowly decreased to 2.7 × 102 mL g−1 with the salinity of 27.5 psu. Combining with the previously published results, it is observed that higher suspended particle (SPM) concentration could enhance the Kd values of 137Cs when SPM was below 12 mg L−1. Our results show that post-depositional mobility of 137Cs in the marine environment, except for river-dominated coastal areas, result in the 137Cs chronology is not suitable to validate the 210Pbex-based chronology. The penetration depths of 137Cs were found to be much deeper than it was expected based on the 137Cs and 239+240Pu peak and 210Pb chronology. Chitin showed a higher affinity for 137Cs than clay particles (e.g., smectite and illite). The desorption experiment showed that the NH4+ could leach 5.6% of sorbed 137Cs, accounting for 79% of the total exchangeable fraction while 2.8% of the total 137Cs was bound to organic matter. These observations support the field observation degradation of organic matter in anoxic marine sediment could enhance the mobility of 137Cs.

Impacts of glacier and sea ice melt on methane pathways on the Northeast Greenland shelf

Global warming has led to a sharp decrease in Arctic summer sea ice extent and a dramatic ice mass loss of the Greenland Ice Sheet over the past three decades. The Northeast Greenland continental shelf is a site of intense water mass transformation involving both sea ice processes and glacier dynamics. The Arctic shelf waters are considered to be a net source of atmospheric methane (CH4); however, the effect of glacier and sea ice melt on oceanic CH4 concentrations still needs to be investigated. To better understand the effect of meltwater on the CH4 budget of the ocean, our study constrains the CH4 pathways by following changes in water mass properties and infers potential CH4 sources and sinks. Based on measurements of concentration and carbon isotope delta (δ13C) of CH4, the water mass tracer δ18O(H2O) and physical properties of the water masses, we detected CH4 excess in surface waters, which we attribute to brine release during sea ice formation. We show that this CH4 excess is sustained throughout the melt season, due to a freshwater lid formed at the ocean surface. The meltwater hardly alters the CH4 excess, but enhances water stratification, which, in turn, restricts the sea-to-air flux. The CH4 excess is subject to mixing with surrounding shelf waters influenced by basal glacial meltwater discharge. We suggest that the CH4 excess of Northeast Greenland continental shelf waters is redistributed in the marine environment, while CH4 emission to the atmosphere is limited to regions not covered by sea ice.

Fine-scale habitat associations of medusae and ctenophores along a gradient of river influence and dissolved oxygen

Environmental drivers of abundance and distribution are poorly described for many gelatinous zooplankton (GZ), yet this knowledge is essential to understanding the role of GZ in ecosystems and potential ecological impacts. In situ imaging systems are a contemporary approach to describe the relationship between GZ and their environment, providing detailed information on distribution and habitat preference. Here we quantify patterns in the abundance and distribution of medusae and ctenophores (>1 cm) related to oceanographic data collected with in situ imaging on the stratified northern Gulf of Mexico shelf. Fourteen taxa were identified, typically to genus level, including ctenophores, scyphomedusae, and hydromedusae. The site with the most freshwater influence and widespread bottom water hypoxia contained the highest taxonomic diversity of GZ, with Aequorea, Chrysaora, and Pelagia occurring only at this site. Although most taxa aggregated in particular oceanographic micro-habitats (e.g., surface, low salinity, high temperature, or deeper, high salinity, low temperature), some were habitat generalists, found evenly dispersed throughout the water column (e.g., Eutima) or bimodally distributed near the surface and bottom (e.g., Liriope). Paired day/night sampling revealed that most taxa did not vertically migrate, suggesting they remain in their preferred micro-habitats for extended periods of time and potentially serve as biological tracers of water masses. Imaging offers the ability to monitor these under-described size classes of GZ with higher taxonomic resolution and describe their fine-scale habitat preferences and vertical migration behaviors, which ultimately improves our understanding of how GZ disperse and interact with other zooplankton in stratified shelf waters.

The Potential of 233U/236U as a Water Mass Tracer in the Arctic Ocean

AbstractThis study explores for the first time the possibilities that the 233U/236U atom ratio offers to distinguish waters of Atlantic or Pacific origin in the Arctic Ocean. Atlantic waters entering the Arctic Ocean often carry an isotopic signature dominantly originating from European reprocessing facilities with some smaller contribution from global fallout nuclides, whereas northern Pacific waters are labeled with nuclides released during the atmospheric nuclear testing period only. In the Arctic Ocean, 233U originates from global fallout while 236U carries both, a global fallout and a prominent nuclear reprocessing signal. Thus, the 233U/236U ratio provides a tool to identify water masses with distinct U sources. In this work, 233U and 236U were analyzed in samples from the GN01 GEOTRACES expedition to the western Arctic Ocean in 2015. The study of depth profiles and surface seawater samples shows that: (a) Pacific and Atlantic waters show enhanced signals of both radionuclides, which can be unraveled based on their 233U/236U signature; and (b) Deep and Bottom Waters show extremely low 233U and 236U concentrations close to or below analytical detection limits with isotopic ratios distinct from known anthropogenic U sources. The comparably high 233U/236U ratios are interpreted as a relative increase of naturally occurring 233U and 236U and thus for gradually reaching natural 233U/236U levels in the deep Arctic Ocean. Our results set the basis for future studies using the 233U/236U ratio to distinguish anthropogenic and pre‐anthropogenic U in the Arctic Ocean and beyond.

Dissolved neodymium isotopes in the Mediterranean Sea

The neodymium isotopic composition (εNd) of seawater is one of the most important geochemical tracers to investigate water mass provenance, which can also serve as a proxy to reconstruct past variations in ocean circulation. Nd isotopes have recently also been used to reconstruct past circulation changes in the Mediterranean Sea on different time scales. However, the modern seawater εNd dataset for the Mediterranean Sea, which these reconstructions are based on, is limited and up to now only 160 isotopic measurements are available for the entire basin. The lack of present-day data also limits our understanding of the processes controlling the Nd cycle and Nd isotopic distribution in this semi-enclosed basin. Here we present new εNd data from 24 depth profiles covering all Mediterranean sub-basins, which significantly increases the available dataset in the Mediterranean Sea. The main goal of our study is to better characterize the relationship between the dissolved Nd isotope distributions and major water masses in the Mediterranean Sea and to investigate the impact and relative importance of local non-conservative modifications, which include input of riverine particles and waters, aeolian-derived material and exchange with the sediments at continental margins. This comprehensive εNd dataset reveals a clear εNd – salinity correlation and a zonal and depth gradient with εNd systematically increasing from the western to the eastern Mediterranean basin (average εNd = −8.8 ± 0.8 and −6.7 ± 1 for the entire water column, respectively), reflecting the large-scale basin circulation. We have evaluated the conservative εNd behaviour in the Mediterranean Sea and quantified the non-conservative components of the εNd signatures by applying an Optimum Multiparameter (OMP) analysis and results from the Parametric Optimum Multiparameter (POMP) analysis of Jullion et al. (2017). The results of the present study combined with previously published Nd isotope values indicate that dissolved εNd behaves overall conservatively in the open Mediterranean Sea and show that its water masses are clearly distinguishable by their Nd isotope signature. However, misfits between measured and OMP- and POMP-derived εNd values exist in almost all sub-basins, especially in the eastern Levantine Basin and Alboran Sea at intermediate-deep depths, which can be explained by the influence of detrital lithogenic εNd signatures through interaction with highly radiogenic Nile sourced volcanic fractions and unradiogenic sediments, respectively.The radiogenic signature acquired in the eastern Levantine Basin is carried by the Levantine Intermediate Water and transferred conservatively to the entire Mediterranean at intermediate depths. Our measured εNd values and OMP- and POMP-derived results indicate that non-conservative contributions originating from sediment sources are then propagated by water mass circulation (with distinct preformed εNd) along the Mediterranean Sea through advection and conservative mixing. Mediterranean εNd effectively traces the mixing between the different water masses in this semi-enclosed basin and is a suitable water mass tracer.

Controlling factors and impacts of river-borne neodymium isotope signatures and rare earth element concentrations supplied to the Canadian Arctic Archipelago

Determining the factors controlling the neodymium (Nd) isotopic compositions (expressed as εNd) and rare earth element (REE) concentrations of rivers is imperative to improve our understanding of the distribution of these water mass tracers in the ocean. Here we present the first measurements of <0.45 μm-filtrate REE concentrations (i.e., the concentration of truly dissolved, nano-particulate and colloidal REEs passing through a 0.45 μm filter, hereafter referred to as dissolved) and εNd in rivers draining into the Canadian Arctic Archipelago (CAA). Results show a large variation in both REE concentrations (Nd=[8;37,260] pmol/kg) and εNd ([−32.1;−15.1]) in the thirteen rivers sampled. Dissolved REE concentrations increase with increasing fractions of metamorphic rocks and ice cover in the rivers' watersheds, while εNd and PAAS-normalized REE patterns are inherited from the watershed's bedrock lithology. The four rivers draining watersheds composed of Precambrian metamorphic rocks exhibit the highest REE concentrations, the least radiogenic εNd, and shale-normalized patterns enriched in light REEs. The remaining nine rivers drain mainly or exclusively sedimentary bedrock and have lower REE concentrations, more radiogenic εNd and generally show heavy REE enrichment, with variable negative cerium (Ce) anomalies. The presence of ice sheets in the drainage area, and the ionic strength, pH, and dissolved organic carbon concentration of river water are the main factors determining riverine dissolved REE concentrations by controlling the formation and stabilization of colloids. We estimate a flow of dissolved Nd transported by Arctic rivers discharging into the CAA equivalent to the Nd flux of seawater entering the CAA. Depending on the percentage of Nd removal during mixing with seawater, the impact of river water on the εNd of seawater exiting the CAA could be modest (if 90% removal) or more significant (if ≪90% removal). This riverine contribution could potentially impart a climate-sensitive εNd signature to the seawater reaching Baffin Bay, with possible implications for the use of εNd in paleoceanographic reconstructions of water mass distribution.

Tracing Water Masses and Assessing Boundary Scavenging Intensity With Beryllium Isotopes in the Northern South China Sea

AbstractThe cosmogenic radionuclide 10Be and its stable isotope 9Be can be used as a tracer for water mass mixing, but such applications are rare in both open oceans and marginal seas. Here we report distributions of dissolved 9Be and 10Be concentrations of the seawater in the surface and water columns along a section from shelf to deep basin in the northern South China Sea (SCS). The concentrations of 9Be and 10Be in surface waters range between 8.8–43.6 pmol/kg and 118–576 atoms/g, respectively. The 9Be in the northern SCS is dominantly sourced from river waters, while 10Be has a prominent input from the western Pacific, resulting in the highest 10Be/9Be ratio of 10.9 × 10−8 closest to the Luzon Strait. Along the depth section, the 9Be concentrations decrease southward while 10Be concentrations increase with the maximum value of 1,237 atoms/g occurring at 2,843 m depth of Station A10. The 10Be/9Be ratios are interpreted with consideration of water mixing and boundary scavenging, which reveal evidence of a branch of the intruding Kuroshio Current (&gt;7.7 × 10−8) in subsurface water and a deep cyclonic current (&gt;8.9 × 10−8). A box model yields a sedimentation flux of 10Be around 1,167 atoms/m2/s, that is, 4.6 times of the atmospheric deposition flux, pointing to active boundary scavenging of 10Be. The residence time of 10Be in the deep water is estimated to be longer than 79 years in the northern SCS. The beryllium isotopes as a water mass tracer will find wide applications in basins where the endmembers are sufficiently differentiated.

Determination of Nd isotopic composition in seawater using newly developed solid phase extraction and MC-ICP-MS

Determination of neodymium (Nd) isotopic composition in seawater is useful for tracing water masses and geochemical cycles for lithogenic elements in the ocean. A new separation procedure for determination of the Nd isotopic composition of in seawater samples was developed that offers enhanced sample throughput and improved measurement reliability. The procedure consists of conventional Fe hydroxide coprecipitation, solid phase extraction using DGA chelating resin column chromatography, and Ln Resin column chromatography to preconcentrate samples. High selectivity in HNO3 medium and elution by low concentration HCl medium for Nd are characteristics of extraction using DGA Resin®, and they allowed an evaporation step to be omitted between the chromatographic steps. These chromatographic steps, using DGA Resin to separate REEs and Ln Resin® to remove Sm, were refined from a previous study. The procedural blank value of Nd was obtained as 2 pg (n = 6) from 3 L of water samples. Chemical yield of Nd from 3 L of seawater ranged within 90–95%. The developed procedure was combined with multiple collector-ICP-MS and applied to analysis of vertical seawater samples obtained from the western subarctic gyre of the North Pacific Ocean, where εNd ranged from −1.29 ± 0.42 at the surface to −3.80 ± 0.41 at 4000 m depth. These results were validated by comparing them with results obtained by the conventional method verified in the GEOTRACES inter-calibration program.

Tracing Water Mass Mixing From the Equatorial to the North Pacific Ocean With Dissolved Neodymium Isotopes and Concentrations

The sluggish water mass transport in the deeper North Pacific Ocean complicates the assessment of formation, spreading and mixing of surface, intermediate and deep-water masses based on standard hydrographic parameters alone. Geochemical tracers sensitive to water mass provenance and mixing allow to better characterize the origin and fate of the prevailing water masses. Here, we present dissolved neodymium (Nd) isotope compositions (εNd) and concentrations ([Nd]) obtained along a longitudinal transect at ∼180°E from ∼7°S to ∼50°N. The strongest contrast in Nd isotope signatures is observed in equatorial regions between surface waters (εNd ∼0 at 4.5°N) and Lower Circumpolar Deep Water (LCDW) prevailing at 4500 m depth (εNd = −6.7 at 7.2°N). The Nd isotope compositions of equatorial surface and subsurface waters are strongly influenced by regional inputs from the volcanic rocks surrounding the Pacific, which facilitates the identification of the source regions of these waters and seasonal changes in their advection along the equator. Highly radiogenic weathering inputs from Papua-New-Guinea control the εNd signature of the equatorial surface waters and strongly alter the εNd signal of Antarctic Intermediate Water (AAIW) by sea water-particle interactions leading to an εNd shift from −5.3 to −1.7 and an increase in [Nd] from 8.5 to 11.0 pmol/kg between 7°S and 15°N. Further north in the open North Pacific, mixing calculations based on εNd, [Nd] and salinity suggest that this modification of the AAIW composition has a strong impact on intermediate water εNd signatures of the entire region allowing for improved identification of the formation regions and pathways of North Pacific Intermediate Water (NPIW). The deep-water Nd isotope signatures indicate a southern Pacific origin and subsequent changes along its trajectory resulting from a combination of water mass mixing, vertical processes and Nd release from seafloor sediments, which precludes Nd isotopes as quantitative tracers of deep-water mass mixing. Moreover, comparison with previously reported data indicates that the Nd isotope signatures and concentrations below 100 m depth essentially remained stable over the past decades, which suggests constant impacts of water mass advection and mixing as well as of non-conservative vertical exchange and bottom release.

Quantifying Climate Signals: Spicity, Orthogonality, and Distance

AbstractThe variability of water masses has been analyzed using temperature and salinity or density and various forms of spicity/spiciness. The objective way of comparing these spicity/spiciness functions is not the difference between these definitions; instead, it is through the application of these functions in tracing water masses and climate signal analysis. The major advantage of the spicity function introduced by Huang et al. Journal of Geophysical Research: Oceans, is that this function in combination with density gives rise to an orthogonal coordinate, in which the signals are separated into two independent components. In addition, a new quantity, distance, is introduced, that can be used to trace water masses both along and across isopycnal surfaces. Spicity can serve as an appropriate tool to extract globally varying water mass properties as a supplement to variations of density alone.

90Sr in seawater of the East China Sea: Inventory, new potential source, and environmental implications

90Sr is useful for tracing water mass movement in oceans. We collected a suit of seawater samples from the East China Sea (ECS) in the May 2011 to investigate the spatial and vertical distribution of 90Sr and to understand its transportation and fate. To understand the sources and transportation of 90Sr more clearly, published 137Cs data from the same cruise were used to obtain the 90Sr/137Cs activity ratios. The results showed that 90Sr activities were controlled by the circulation system of the ECS, with high values in coastal regions and low values in oceanic waters. The plume with a high 90Sr/137Cs ratio showed that in late spring, the Changjiang Diluted Water could flow southeastward and extend to 126–127° E, which is farther than the previously known value of 124° E. The high 90Sr/137Cs ratios (1.35 ± 0.62) and a long effective half-life of 90Sr (20.0 ± 0.3 y) in the ECS surface water revealed that 90Sr is surplus in comparison with 137Cs. However, historical variations in the 90Sr/137Cs ratio seem to preclude the simple explanation that riverine input causes a 90Sr surplus in the ECS. Groundwater discharge with a high 90Sr but very low 137Cs may be a new potential source. However, it is difficult to quantify the contribution of groundwater discharge at present, and more detailed studies are required in this regard. Additionally, we compiled 90Sr and 137Cs water column inventory data in the western North Pacific and found that the cumulative fallout onto the ocean was different from that on land in the 20–40° N band.