The silicon stable isotope distribution along the GEOVIDE section of the North Atlantic Ocean

The stable isotope composition of dissolved silicon in seawater (δSiDSi) was examined at 10 stations along the 10 GEOVIDE section, spanning the North Atlantic Ocean (40°N-60°N) and Labrador Sea. Near-surface water δSiDSi could not be evaluated due to the very low dissolved silicon (DSi) concentrations (< 5 M). However, variations in δSiDSi below 500 m were closely tied to the distribution of water masses. Higher δSiDSi values are associated with intermediate and deep water masses of northern Atlantic or Arctic Ocean origin, whilst lower δSiDSi values are associated with DSi-rich waters sourced ultimately from the Southern Ocean. Correspondingly, the lowest δSiDSi values were observed in the deep and abyssal eastern 15 North Atlantic, where dense southern-sourced waters dominate. The extent to which the spreading of water masses influences the δSiDSi distribution is marked clearly by Labrador Sea Water (LSW), whose high δSiDSi signature is visible not only within its region of formation within the Labrador and Irminger Seas, but also throughout the mid-depth western and eastern North Atlantic Ocean. Both δSiDSi and hydrographic parameters document the circulation of LSW into the eastern North Atlantic, where it overlies southern-sourced Lower Deep Water. The GEOVIDE δSiDSi distribution thus provides a clear 20 view of the direct interaction between subpolar/polar water masses of northern and southern origin, and allow examination of the extent to which these far-field signals influence the local δSiDSi distribution.


Introduction
Proxies of nutrient utilisation, such as the silicon stable isotopic composition ( 30 Si) of diatom silica, provide a means of reconstructing the past behaviour of marine nutrient cycles, giving insight into the strength of the biological pump in the past, 25 and its influence over atmospheric concentrations of CO2.However, diatom silica  30 Si does not depend solely on the degree of utilisation of dissolved silicon (DSi) at the ocean's surface, but also on the  30 Si value of its source DSi.Since the  30 Si of DSi (δ 30 SiDSi) at any given location in the ocean results from the combined effects of biological uptake of dissolved silicon, dissolution of sinking biogenic silica, and meso-to macro-scale features of ocean circulation, successfully reconstructing past Biogeosciences Discuss., https://doi.org/10.5194/bg-2018-165Manuscript under review for journal Biogeosciences Discussion started: 16 April 2018 c Author(s) 2018.CC BY 4.0 License.

Sample collection and processing
Samples were collected aboard the R/V Pourquoi Pas? during GEOVIDE.The cruise began on May 15, 2014 in Lisbon, Portugal, headed north towards Greenland, and then traversed south-west to St. John's, Canada, arriving on June 30, 2014 (Fig. 1). 5 Seawater samples for  30 SiDSi analysis were collected using Niskin bottles attached to a standard rosette conductivitytemperature-depth (CTD) unit from 10 locations in the North Atlantic Ocean and Labrador Sea (Fig. 1 and Table 1).Samples were filtered through polycarbonate 0.45 m filters (Millipore) and stored in acid-cleaned, low-density polyethylene bottles at room temperature.10 The DSi concentration of all samples collected (n = 56) was determined via molybdate blue spectrophotometry (Strickland and Parsons, 1972).For the measurement of  30 SiDSi, DSi was extracted from the seawater by precipitating it as trimethylamine silicomolybdate, which was subsequently combusted to form SiO2 (De La Rocha et al., 1996).This SiO2 was dissolved at room temperature in polypropylene microcentrifuge tubes (1.5 mL) containing 23 M HF (Suprapur) to yield a final solution 15 concentration of 0.23 M Si (e.g. 4 mol of SiO2 dissolved in 17.4 L of HF).

Purification
Every sample was further purified using ion exchange chromatography following Engström et al. (2006).Briefly, 17.4 L of a 0.23 M Si solution was diluted in 7.7 mL of Ultra Hiqh Quality water (UHQ H2O; 18.2 MΩ-cm; Millipore Direct-Q) and loaded onto columns containing AG 1-X8 resin (BioRad) that had been preconditioned with 2 M NaOH.The sample matrix 20 was eluted using 95 mM HCl + 23 mM HF followed by the elution of the purified Si using 0.14 M HNO3 + 5.6 mM HF.All acids were Suprapur (Merck) and were diluted with UHQ H2O.

Isotopic measurements
Silicon stable isotope composition ( 30 Si) of the purified samples was measured using standard-sample bracketing combined with external normalisation by doping the samples with magnesium (Mg) (e.g., Cardinal et al., 2003) on a Thermo Scientific 25 Neptune multi-collector inductively-coupled plasma mass spectrometer (MC-ICP-MS) at the Unité Géosciences Marines (Ifremer, Plouzané).Prior to the isotopic analysis, the purified samples were diluted with 0.16 M HNO3 (1 % HNO3) to 1 ppm Si, yielding a roughly 12 V signal on mass 28 at medium resolution (see Table 2 for additional information on operating conditions).All samples and standards (NBS28 and a 99.995 % pure silica sand (Alfa Aesar) used as a working standard) were passed through column chemistry and matrix-matched to give the same signal strength (within 10 %) and to contain the same 30 amount of HF (generally 1 mM).Magnesium (1000 ppm, NIST SRM) was added to the samples and standards just prior to Biogeosciences Discuss., https://doi.org/10.5194/bg-2018-165Manuscript under review for journal Biogeosciences Discussion started: 16 April 2018 c Author(s) 2018.CC BY 4.0 License.measurement at a final concentration of 0.1 ppm (Cardinal et al., 2003;Abraham et al., 2008).Si solutions were introduced into the plasma via an Apex desolvating system equipped with a PFA nebulizer (uptake rate = 100 μL min -1 ) without additional gas.
For each measurement, beam intensities at masses 25 and 26 (Mg),and 28,29,and 30 (Si) were monitored in dynamic mode 5 (i.e.switching between Si and Mg masses) for one block of 25 cycles of 8-second integrations.Five minutes of rinse with 2 % HNO3 followed each sample and each standard solution.Solutions were analyzed in medium resolution mode (m/Δm > 6000).
Using a standard-sample-standard bracketing technique,  30 Si values for the samples were expressed as follows: (1) 10 The Si isotope ratios in Eqn. 1 above ( 30 Si/ 28 Si and 29 Si/ 28 Si) were corrected for mass bias by external normalisation using Mg doping.For example, the corrected 30 Si to 28 Si ratio ( 30 Si/ 28 Si)corr is: ( 30 Si/ 28 Si)corr = ( 30 Si/ 28 Si)meas x ( 30 SiAM 28 SiAM) Mg (2) 15 Where ( 30 Si/ 28 Si)meas is the measured ratio, 30 SiAM and 28 SiAM are the atomic masses of 30  (3) 20 where 25 MgA/ 26 MgA is the expected ratio of the natural abundances of the isotopes, ( 25 Mg/ 26 Mg)meas is the measured ratio, and 25 MgAM and 26 MgAM are the atomic masses of 25 Mg and 26 Mg respectively.Each measurement of a sample fell between two measurements of the standard, and each sample was measured three times.This total of three sample measurements and five standard measurements was repeated 2-3 times in each mass spectrometry session and used to calculate one replicate value of 25  30 Si and  29 Si.As discussed below, full chemistry replicates were routine for each sample (see Table S2).
Interference-free measurement was ensured by checking that δ 29 Si and δ 30 Si for all samples was consistent with the mass dependent fractionation line (Fig. 2).The signal was optimized to reduce the 14 N 16 O interference on m/z 30 to below 0.5 % of the 30 Si peak.Measurements were performed on the low-mass side of the peak where interference is minimal.Blanks were 30 maintained below 1 % of the main signal and were subtracted for each sample and standard.Long-term reproducibility and accuracy on δ 30 Si values of the analytical procedure were assessed using the standard deviation of 54 analyses of NBS28 and 29 analyses of a secondary reference standard (Silicon (IV) oxide, Alfa Aesar) generated over 6 years (±0.10 ‰, 2).Reproducibility of the full chemical and analytical procedure was estimated using at least one replicate of each sample (chemical preparation plus isotopic measurements) and average reproducibility on replicate δ 30 Si was ±0.10 ‰ (2).
Measurements of Big Batch (n = 3) produced an average value of -10.48 ± 0.34 (2), well within the range of intercalibration values reported by Reynolds et al. (2007).Measurement of the US GEOTRACES intercalibration reference seawater standard from the Aloha Station (1000 m) gave a  30 SiDSi value of +1.16 ± 0.16 ‰ (2n = 3), within the range of intercalibration 5 values (1.24 ± 0.20 ‰;Grasse et al., 2017).Measurement of the Canada/GEOVIDE GEOTRACES intercalibration samples, where duplicate samples at 3 depths and 2 stations were analysed by two different laboratories (Ifremer Plouzané and ETH Zurich), conforming to the GEOTRACES intercalibration protocol for a cruise without a cross-over station, gave similar  30 SiDSi values (see Table 3).Note that ETH Zurich uses a different purification method (cation exchange resin, see de Souza et al., 2012b) and MC-ICPMS instrument (Nu Plasma 1700) than Ifremer Plouzané (described in section 2.2).The methods 10 for each laboratory that participated in Canada/GEOVIDE GEOTRACES intercalibration study are also presented in the US GEOTRACES intercalibration study (Grasse et al., 2017).

Optimum Multiparameter Analysis to determine the water mass structure in the North Atlantic Ocean
In order to accurately examine the relationship between the distribution of  30 SiDSi and water masses, the results of the Optimum Multiparameter (OMP) analysis of García-Ibáñez et al. (2017;this issue) were used to identify the mixture of water 15 masses present within each sample and their contribution to the DSi budget.
The upper layers of the GEOVIDE section were represented by the North Atlantic Central Waters (NACW), transported by the North Atlantic Current (NAC; Pollard et al., 1996), and Subpolar Mode Waters (SPMW), the end-product of the transformation of NACW through air-sea interaction (McCartney and Talley, 1982;Tsuchiya et al., 1992).To account for the 20 change in the temperature of SPMW along the path of the NAC as the result of air-sea interaction, two SPMWs were differentiated: IcSPMW (Iceland-Subpolar Mode Water) and IrSPMW (Irminger-Subpolar Mode Water).The intermediate layers of the section were represented by LSW, Mediterranean Water (MW), Subarctic Intermediate Water (SAIW), and Polar Intermediate Water (PIW).LSW is the last stage of the transformation of SPMWs and forms in the Labrador and Irminger Seas (e.g., Pickart et al., 2003;de Jong and de Steur, 2016;Fröb et al., 2016).MW enters the North Atlantic from the 25 Mediterranean Sea through the Strait of Gibraltar (Ambar and Howe, 1979;Baringer and Price, 1997).SAIW originates in the Labrador Current by mixing of the NAC waters with LSW (Iselin, 1936;Arhan, 1990;Read, 2000).The deep layers of the section were represented by Denmark Strait Overflow Water (DSOW), Iceland-Scotland Overflow Water (ISOW), North East Atlantic Deep Water (NEADW) and Lower Deep Water (LDW).Overflow waters (DSOW and ISOW) form after the deep waters of the Nordic Seas flow over the Greenland-Iceland-Scotland sills and entrain Atlantic waters (van Aken and de Boer, 30 1995;Read, 2000;Dickson et al., 2002;Fogelqvist et al., 2003;Yashayaev and Dickson, 2008).NEADW is formed as a result of entrainment events that occur along the journey of ISOW through the Iceland Basin (van Aken, 2000).NEADW recirculates Biogeosciences Discuss., https://doi.org/10.5194/bg-2018-165Manuscript under review for journal Biogeosciences Discussion started: 16 April 2018 c Author(s) 2018.CC BY 4.0 License.
in the West European Basin and mixes with the surrounding waters, including the Antarctic Bottom Water (AABW) (van Aken and Becker, 1996), resulting in the formation of LDW.

Water column profiles of DSi
Dissolved silica concentrations below 500 m along the GEOVIDE section ranged from 7 to 47 M (Fig. 3a).The stations 5 located to the east of the Mid-Atlantic Ridge (MAR; STN 01, STN 13,STN 21,STN 26,STN 32) show DSi increasing in concentration from < 10 M to 20-50 M below about 2000 m (Fig. 3a).Stations located to the west of the MAR (STN 44,STN 60,STN 64,STN 69,and STN 70) show only slight increases in DSi concentration with depth, with most of the values falling between 9-12 M (Fig. 3a).This difference relates to the distribution of water masses in the northern North Atlantic, with the predominance of the most egregiously Si-poor northern-sourced water masses (LSW, ISOW/NEADW, DSOW) 10 predominating in the western Atlantic while abyssal layers in the eastern Atlantic have had more of a contribution from Sirich southern-sourced waters (LDW) (see Section 4.1).A clear pattern in the DSi concentration throughout the water column is that the eastern profiles exhibit a more typically "nutrient-like" profile than in the western profiles (Supplementary Table S1; Fig. 3a).
Our data agree with the systematics of these two studies, with each data set exhibiting nearly identical linear regressions, except for the value of the y-intercept, which appear to result from a near-constant offset between  30 SiDSi values measured at different laboratories (see Fig. 4).Similar offsets were observed and discussed by Brzezinski and Jones (2015), Such offsets 15 of order ±0.2 ‰ have been recognized to exist between seawater  30 Si data produced in different laboratories; their origin remains unclear, although they may have to do with differences in sample processing and chemical purification.The offset to the data of de Souza et al. ( 2012b), produced at ETH Zurich, is somewhat surprising given the good agreement in  30 SiDSi for 6 seawater samples analyzed both at Plouzané and Zurich, but a small offset to lower  30 SiDSi at Plouzané is consistent with the offset (0.1 ‰) in these two laboratories' mean  30 SiDSi values for the seawater reference Aloha-1000 (Grasse et al., 2017).20 Whilst not ideal for the determination of the absolute  30 SiDSi value for each basin, the existence of such interlaboratory offsets does not impair our ability to analyze the distribution of  30 SiDSi along the GEOVIDE transect, with the systematics of our data exhibiting nearly-identical behaviour to previously-published studies (Fig. 4).we discuss our  30 SiDSi dataset in the context of regional oceanography, in order to study the control of interacting interior water masses on the  30 SiDSi distribution of the high North Atlantic.
4.2 Relationship between North Atlantic  30 SiDSi distribution and water mass structure The GEOVIDE section intersects numerous water masses of various origins whose presence is reflected in the distributions of salinity, dissolved oxygen (O2), and potential vorticity (PV) along the section (Fig. 5a, b, c; dissolved O2 is presented as percent 5 saturation, i.e., O2/O2 sat × 100, where O2 sat is the saturation O2 concentration).Since  30 SiDSi was only measured at depths below 500 m, we focus on the intermediate and deep ocean water masses.In discussing the relationship between the  30 SiDSi distribution and water mass structure, we initially focus on the western-and easternmost sections of the GEOVIDE transect, where water masses are in their most unadulterated form along the transect, prior to discussing their extension into the mid-

Atlantic. 10
Starting with the westernmost profiles, those of STNs 77, 69, and 64 in the Labrador Sea, we see relatively well-oxygenated waters with low PV (Fig. 5) extending to depths below 2000 m, reflecting the presence of LSW.This water mass, which contributes to NADW, is formed by deep convection in the Labrador and Irminger Seas (e.g., de Jong and de Steur, 2016) and spreads across the North Atlantic at intermediate to mid-depths (see Fig. 1).Two distinct types of LSW can be distinguished 15 and are indeed visible in our profiles.There is an extremely-low-PV (< 4×10 -12 m -1 s -1 ) and well-oxygenated (> 90 % saturation) pycnostad extending from around 400 m to 1200 m in the Labrador and Irminger Basins, and a saltier, less well-oxygenated water mass observed from roughly 1500 m to 2300 m.These two water masses have been called Upper and Lower LSW, respectively (e.g., Kieke et al., 2007), and reflect variability in the severity of heat loss and depth of convection in the Labrador Sea (Yashayaev et al., 2003;2007) most likely associated with differences in atmospheric forcing during different phases of 20 the North Atlantic Oscillation (NAO; Dickson et al., 1996;Lazier et al., 2002).
At the three stations in the Labrador Sea, Upper LSW has a  30 SiDSi of around +2 ‰ and a DSi concentration of < 10 µM (Fig 3).Lower LSW has slightly lower  30 SiDSi values (around +1.5 ‰) and slightly higher DSi concentrations (~10-15 µM).These differences could be due to a slightly greater proportion of regenerated silica in these deeper layers, less frequently and 25 intensively penetrated by deep convection, or to differences in the preformed properties of Upper and Lower LSW, a result of convection to greater depths during the formation of Lower LSW.
Below LSW, the central Labrador Sea (STN 69) exhibits an exemplary "stacking" of the water masses contributing to NADW.
Specifically, an increase in salinity at 3000 m points to the presence of NEADW, a modified version of the eastern Atlantic 30 overflow water mass ISOW (van Aken and de Boer, 1995) that has crossed into the western Atlantic at the Charlie-Gibbs Fracture Zone (van Aken, 2000).At this point, NEADW has a  30 SiDSi of +1.values essentially equal to that of Lower LSW since ISOW has entrained LSW during its journey from the Iceland-Scotland sill.At the very base of the water column, beginning at about 3500 m water depth, a decrease in salinity and increase in O2 saturation point to the presence of DSOW, which flows from the Arctic Ocean into the North Atlantic as a bottom-hugging overflow off the eastern coast of Greenland, and represents the densest water contributing to NADW (Dickson and Brown, 1994).Our 30 SiDSi sample is situated within the transition between NEADW and DSOW, with slightly lower DSi than in 5 NEADW, but no distinguishable difference in terms of its  30 SiDSi value of around +1.5 ‰.
Moving eastwards along the GEOVIDE transect brings us next to STN 60, on the southeastern coast of Greenland.This relatively shallow station has sampled IrSPMW at its upper two depths, which have high  30 SiDSi values (2.8 ‰ at 1000 m and 1.8 ‰ at 1400 m) and relatively low DSi concentrations (around 10 µM), reflective of the mixing of nutrient-depleted surface 10 waters into this water mass.Subpolar Mode Waters can be seen as precursors to LSW, as they form pycnostads of progressively greater density from east to west in the subarctic gyre, preconditioning the upper water column for deep-reaching Labrador Sea convection by producing a relatively unstratified water column (Brambilla and Talley, 2008).Their more elevated  30 SiDSi values than that of LSW imply that the entrainment of DSi during deep convection associated with LSW formation plays an important role in setting the final  30 SiDSi signature of this water mass.The deepest depth sampled at STN 60 (1800 m), on the 15 other hand, is probably LSW, with its low PV, high O2, and  30 SiDSi around +1.4 ‰, similar to the value observed in the central Labrador Sea.
Moving all the way across the Atlantic to the easternmost portion of the GEOVIDE transect allows us to focus in on two more important interior water masses.One of the most striking features in the distributions of salinity and O2 is the tongue of salty, 20 O2-poor water extending westward from the Iberian margin at about 1000 m water depth.This is predominantly MW that has entered the Atlantic through the Strait of Gibraltar (Iorga and Lozier, 1999).The one sample we have of predominantly MW is at 1000 m depth at STN 01, just off of the Iberian Peninsula, with a  30 SiDSi of +1.2 ‰ and a DSi concentration of about 10 µM.The  30 SiDSi value of +1.2 ‰ corresponds well to the value of +1.3 ‰ measured by Coffineau (2013) in samples from closer to the point of origin of this water mass.25 The other water mass sampled for  30 SiDSi in the eastern Atlantic Ocean is an O2-poor, low-PV, Si-rich abyssal water mass that is present below about 3000 m.This is LDW (McCartney, 1992), which derives from northward-flowing AABW that has entered the eastern Atlantic Ocean via the Vema Fracture Zone (Mantyla and Reid, 1983;McCartney et al., 1991).The OMP results of García-Ibáñez et al. (2017;this issue) shown in Fig. 5d nicely illustrate that LDW (which they denote as NEADWL) 30 is the dominant contributor to the DSi inventory of the deep eastern Atlantic.This is a direct result of LDW being rich in DSi The remaining three stations in the mid-Atlantic (2238°W; STNs.26, 32 and 44) are influenced by varying combinations of the water masses of northern and southern origin that were discussed above.The easternmost of these three stations, STN 26 at the edge of the Porcupine Abyssal Plain, provides an exemplary illustration of the interaction of these water masses.At 10 depths of 1400 and 2000 m, the water column at this station is dominated by Lower LSW, as reflected by the PV, O2 and salinity distributions (Fig. 5a, b, c).As in the Labrador Sea itself, Lower LSW bears an elevated  30 SiDSi value, here about +1.7 ‰, and a relatively low DSi concentration of ~15 µM.This Si-poor water mass is underlain, at the very bottom of the profile (3500 m) by the Si-rich southern-sourced LDW (45 M DSi) that bears a typically low  30 SiDSi value of +1.1 ‰.

15
The influence of dense LDW does not extend further west than the Porcupine Abyssal Plain, and thus at stations 44 and 32, Upper and Lower LSW give way to the denser ISOW (or its modified product, NEADW) with depth.As it flows over the Iceland-Scotland Ridge, ISOW mixes with more saline waters of the Atlantic thermocline to form NEADW that, being quite dense, comes to lie below LSW as it flows geostrophically along the western edge of the West European Basin (Fig. 1).The differences in DSi concentration and  30 SiDSi between these northern-sourced water masses are small: ISOW-influenced waters 20 at depths of 2500-3000 m bear values of +1.4 to +1.5 ‰ for  30 SiDSi and 15-25 µM for DSi, whilst LSW is only slightly more DSi-poor and correspondingly higher in  30 SiDSi (10-12 M and +1.4 to +1.9 ‰, respectively).The resemblance in DSi concentration and  30 SiDSi between these two water masses is also due to the entrainment of LSW into ISOW.Interestingly, the very base of the water column at STN 44 is occupied by the dense and Si-poor DSOW, where it has a dissolved silicon concentration of about 8 µM and a  30 SiDSi of +1.2 ‰.Although the DSi is typical for DSOW, the  30 SiDSi value of +1.2 ‰ is 25 unexpectedly low for this water mass.

The influence of Labrador Sea Water on the North Atlantic distribution of  30 SiDSi
The most important isotope fractionation signal in marine DSi is produced by diatom DSi uptake in the surface ocean (De La Rocha et al., 1997;Varela et al., 2004;Sutton et al., 2013), due to the dominant importance of these phytoplankton for the marine Si cycle (Tréguer and De La Rocha, 2013;Hendry and Brzezinski, 2014).As a result, elevated values of  30 SiDSi can 30 be produced only within the well-lit surface ocean, where photosynthesising organisms can grow and silicify.This surfaceocean signal is communicated more broadly by the process of water mass subduction, i.e., the transport of surface water parcels Biogeosciences Discuss., https://doi.org/10.5194/bg-2018-165Manuscript under review for journal Biogeosciences Discussion started: 16 April 2018 c Author(s) 2018.CC BY 4.0 License.into the ocean interior (Stommel, 1979).This is seen particularly clearly in our dataset, which spans a region in which exceptionally deep winter convection gives rise to mixed layers over 1 km deep in the Labrador Sea and Irminger Sea, injecting isotopically fractionated DSi into the ocean interior.
As can be seen from Fig. 5, there is a clear association of elevated  30 SiDSi values with the low-PV and high-O2 signal of LSW, 5 the water mass that is produced by deep winter convection.Indeed, the eastward spread of these elevated values coincides remarkably well with the extension of LSW mapped by McCartney and Talley (1982) based on PV (as shown in Fig. 1).The influence of LSW on the North Atlantic  30 SiDSi distribution is also nicely illustrated by the depth profiles in Fig. 3b Thus, one proximal physical control on the North Atlantic  30 SiDSi distribution is the vertical transport of DSi from the surface ocean to mid-depths during LSW formation.Another physical control is shown by the close correlation between elevated 15  30 SiDSi and lower PV even within the eastern Atlantic Ocean, far from the region of deep convection (Fig. 5).This highlights the fact that the spreading of LSW as a result of the regional circulation transports its isotopic signal within the ocean interior, resulting in mid-depth  30 SiDSi values around +1.5 ‰ in regions where the physical signatures of LSW can be seen, documenting the importance of water mass structure on the marine  30 SiDSi distribution.Furthermore, this circulation pattern results in the direct interaction of this northern-sourced water mass with the southern-sourced LDW, producing strong local 20  (Varela et al. 2016).Both Brzezinski and Jones (2015) and Varela et al. (2016) suggest that this feature results from the nature of the inflows to the Arctic Ocean, which 30 receives isotopically fractionated DSi via the upper-ocean inflows from the Atlantic (and, to a lesser extent, the Pacific) due to the shallow sills that form its boundaries to these ocean basins.Observational and modelling studies indicate that these inflows are isotopically heavy primarily due to isotope fractionation during diatom DSi uptake in the Southern Ocean, although Biogeosciences Discuss., https://doi.org/10.5194/bg-2018-165Manuscript under review for journal Biogeosciences Discussion started: 16 April 2018 c Author(s) 2018.CC BY 4.0 License.more proximal fractionation within the Atlantic and Pacific Oceans most likely also plays some role (de Souza et al., 2012a;2015).
Finally, interesting insights may be gained from a comparison of our Labrador Sea data with the only other published data from this region (de Souza et al., 2012b).Fig. 6 compares data from the central Labrador Sea (STN 69) from the GEOVIDE 5 study with literature data from within the Labrador Sea and slightly further south, in the vicinity of the Grand Banks (de Souza et al., 2012b), tracing LSW and NADW as they flow southwards.The three profiles agree within uncertainty at mid-depths and below, but diverge in the upper ocean at depths associated with Upper LSW.Since deep winter convection occurs up to depths of 1000 -1500 m regularly within the Labrador Sea, this water mass is frequently ventilated locally, which may result not only in variable physical properties (as shown in Fig. 5a,b,c) but also changes in its chemical characteristics, such as 10  30 SiDSi.However, care should be taken not to over-interpret such differences of ~0.3 ‰, given the potential for  30 SiDSi offsets between laboratories of ±0.2 ‰, as discussed in Section 4.1 (Reynolds et al., 2007;Grasse et al. 2017).

Conclusion
Water mass subduction and circulation appears to be the dominant process influencing the distribution of DSi in the North Atlantic Ocean and Labrador Sea.Our dataset of  30 SiDSi along the GEOVIDE transect documents the extent to which the 15 distribution of   SiDSi in the North Atlantic Ocean and Labrador Sea is influenced by the hydrography of this region.At depths below 1000 m, the distribution of   SiDSi is clearly linked to water mass structure, with the two dominant influences coming from northern-sourced waters (LSW and ISOW) and southern-sourced waters (LDW).The Si-poor northern-sourced waters impart the intermediate and mid-depth North Atlantic Ocean with elevated  30 SiDSi values over +1.4 ‰ and up to +1.9 ‰, whilst the Si-rich abyssal LDW results in low  30 SiDSi values of +1.1 ‰ to +1.3 ‰ in the deepest eastern Atlantic Ocean.By 20 combining our isotope data with hydrographic information and results from an optimum multiparameter analysis, we show that the  30 SiDSi distribution bears clear evidence of the influence of LSW flowing across the Atlantic Ocean into the eastern basins, in a manner consistent with McCartney and Talley's (1982) canonical map of the extent of this water mass.As a result, the eastern Atlantic exhibits the direct "stacking" of young, Si-poor LSW above old, Si-rich LDW, producing a range in deep ocean  30 SiDSi values within this one ocean basin that is comparable to that observed over the entire latitudinal range of the 25     (McCartney, 1992;Dickson and Brown, 1994;Lambelet et al., 2016; see also García-Ibáñez et al., 2017;this issue).
show high values (above +1.5 ‰) extending below 2000 m water depth.These high values reach the bottom within the central Labrador Sea (STN 69).Elevated  30 SiDSi values at depths between 1000-2000 m can be found at all stations in the Irminger Basin and extend eastwards into the western portion of the West European Basin (up to STN 26), but the mid-depths of the far eastern Atlantic are marked by lower  30 SiDSi values around +1 ‰.Atlantic  30 SiDSi systematics in a basin-wide context The deep Atlantic Ocean below 1000 m exhibits a wide variation in DSi concentrations, ranging from ~10 M in the middepths of the subpolar North Atlantic Ocean to ~120 M in the abyssal southern Atlantic.Since at least the work of Broecker Biogeosciences Discuss., https://doi.org/10.5194/bg-2018-165Manuscript under review for journal Biogeosciences Discussion started: 16 April 2018 c Author(s) 2018.CC BY 4.0 License.and Takahashi (1980), it has been known that this variation is primarily brought about by the quasi-conservative mixing of DSi between Si-rich abyssal waters derived from the Southern Ocean and Si-poor waters of North Atlantic origin.The analysis of Sarmiento et al. (2007), which takes the effects of water mass mixing into account, has shown that the effect of opal dissolution on deep Atlantic DSi is resolvable, but plays a near-negligible role in controlling the deep DSi distribution.5 The first systematic study of the Atlantic  30 SiDSi distribution (de Souza et al., 2012b) showed that the quasi-conservative behaviour of DSi is clearly reflected by the  30 SiDSi of the deep Atlantic Ocean.Surveying deep water over a wide range of latitudes within the Atlantic Ocean, they found that values of  30 SiDSi vary coherently from high values in the Si-poor waters that contribute to NADW to low values in the Si-rich Southern Ocean deep waters (Fig. 4).The more recent work of Brzezinski and Jones (2015) found identical behaviour within Atlantic deep waters along a near-zonal transect across the subtropical 10 Factoring out the offset in absolute 30 SiDSi values, it is interesting to note that our deep North Atlantic samples exhibit 25 essentially the same  30 SiDSi range (~0.6 ‰; Fig.4) as that observed over the entire latitudinal range of the Atlantic Ocean (deSouza et al., 2012b).Our dataset thus indicates that DSi in the North Atlantic Ocean is an important source of isotopic variability in the deep ocean.This is at least partially due to the transport of isotopically heavy DSi to the North Atlantic by northward-flowing Subantarctic Mode Water / Antarctic Intermediate Water (de Souza et a., 2012b; 2015) and its incorporation into NADW, e.g., during the formation of LSW.However,Brzezinski and Jones (2015) hypothesized that the Arctic Ocean 30 may also play an important role in producing deep North Atlantic  30 SiDSi variability, via overflows across the Greenland-Iceland-Scotland ridge (i.e., DSOW and ISOW), which dominantly contribute to Lower NADW.It thus remains to be understood how the isotopic compositions of various precursors of NADW contribute to its isotopic signal.In the following, Biogeosciences Discuss., https://doi.org/10.5194/bg-2018-165Manuscript under review for journal Biogeosciences Discussion started: 16 April 2018 c Author(s) 2018.CC BY 4.0 License.

( 25 -
45 M) when compared to the other water masses in the North Atlantic Ocean.Biogeosciences Discuss., https://doi.org/10.5194/bg-2018-165Manuscript under review for journal Biogeosciences Discussion started: 16 April 2018 c Author(s) 2018.CC BY 4.0 License.The influence of this Si-rich southern-sourced water mass is also clearly seen in the  30 SiDSi distribution (Fig 3b):  30 SiDSi values below 3000 m in the far-eastern Atlantic (STNs.01, 13 and 21) range from +1.0 ‰ to +1.3 ‰, significantly lower than values at similar depths in the western Atlantic, which is dominated by northern-sourced water masses.The low  30 SiDSi values we observe for LDW compare very well with the value of +1.2 ‰ observed in AABW in the South Atlantic (de Souza et al., 2012b), indicating that the Si-richness of this water mass makes its  30 SiDSi value insensitive to mixing or opal dissolution as 5 it flows northwards in the abyssal Atlantic Ocean.
, which show that, unlike the eastern Atlantic with low  30 SiDSi values at mid-depths, the central and western North Atlantic bears elevated  30 SiDSi values close to those observed within the Labrador Sea itself.Such high values at mid-depths are unique to 10 the North Atlantic Ocean amongst the major open-ocean basins, and result from the local formation of deep waters from Sidepleted surface waters of the subpolar North Atlantic.


30 SiDSi gradients whose systematics correspond nicely to the basin-scale systematics (60°S to 60°N) documented by de Souza et al. (2012b; see Section 4.1 and Fig. 4).Elevated values of  30 SiDSi are also associated with the dense overflows from the Nordic Seas.Whilst our single sample of DSOW surprisingly bears a low  30 SiDSi value of +1.2 ‰, ISOW and its derivative NEADW bear similarly low DSi 25 concentrations and similarly elevated  30 SiDSi values as LSW, reaching up to +1.5 ‰ in the abyssal Labrador Sea.They originate as dense bottom-hugging overflows of mid-depth Nordic Sea waters, influenced by the Arctic Ocean, that enter the North Atlantic across the submarine sills running between Greenland, Iceland and Scotland, and the elevated  30 SiDSi values of ISOW and NEADW reflect the isotopically-heavy nature of the deep Arctic
Figure 1.Map showing the sampling locations from the GEOVIDE voyage, overlain on a schematic of the intermediate and deep ocean circulation.Pink shading indicates the spreading of Labrador Sea Water (LSW) as documented by the extent of a water column minimum potential vorticity of 8×10 -12 m -1 s -1 (McCartney, 1992).Dark blue arrows represent bottom-hugging 5 Nordic Sea Overflows (ISOW and DSOW), pink arrows represent LSW, and orange arrows represent Lower Deep Water

Figure 4 .
Figure 4.  30 SiDSi versus the inverse of DSi concentration for this study (black circles), de Souza et al. (2012b; grey circles) 15 and Brzezinksi and Jones (2015; open circles) for waters > 1000 m depth.Equations reported in the figure refer to linear regressions produced for each dataset.

Figure 5 . 25 Figure 6 .
Figure 5. Depth section across the GEOVIDE transect with hydrographic parameters (a) salinity, (b) oxygen (O2) saturation and (c) potential vorticity (PV), together with (d)  30 SiDSi data overlain by pie charts of the fraction of DSi in each sample 20 contributed by various water masses, as calculated by OMP analysis (García-Ibáñez et al., 2017; this issue).Spreading of Labrador Sea Water, reflected in hydrography by low-salinity, low-PV, high-O2 signals (panels a,b,c) and in the OMP results by a dominant Si contribution from this water mass (panel d), produces a mid-depth extension of elevated  30 Si values into the eastern Atlantic (panel d).For water mass abbreviations see main text (Section 2.4).

Table 1 .
Sampling locations from the GEOVIDE voyage in the North Atlantic Ocean and Labrador Sea (Stations 1-77) and GEOVIDE/Canada GEOTRACES intercalibration stations (Stations K1 and LS2).