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bottom waters are < 20 µmol kg −1 .However, off the shelf along the continental margin the mean C : N : P : O 2 ratio is again close to the Redfield stoichiometry.Comparing the situation of 2011 with nutrient concentration data measured during 2 cruises in 2008 and 2009 implies that the amount of excess P that is created in the bottom waters on the shelf and its export into the subtropical gyre after upwelling varies through time.The magnitude of excess P formation and export is governed by inputs of excess N along with the South Atlantic Central Water (SACW) flowing into the NBUS from the north as a poleward compensation current.Since excess N is produced by the remineralization of N-enriched biomass built up by N 2 -fixing organisms, factors controlling N 2 fixation north of the BUS need to be addressed in future studies to better understand the NBUS' role as P source and N sink in the coupled C : N : P cycles.

Introduction
The biological carbon pump is the term used for the production of organic carbon from dissolved carbon dioxide (CO 2 ) in the surface mixed layer of the ocean and its transport into the large CO 2 reservoir of the ocean beneath the mixed layer.It is both driven and limited by the availability of macronutrients, such as carbon (C), fixed nitrogen (N), and phosphate (P), as well as micronutrients such as iron (Watson et al., 2000;Behrenfeld et al., 2006b).Macronutrients are required in specific stoichiometric ratios for the photosynthetic production of organic matter traditionally termed as Redfield ratio of C : N : P = 106 : 16 : 1 (Redfield et al., 1963).Changes of the Redfield ratio could strongly influence the marine productivity and the oceans' ability to sequester CO 2 from the atmosphere (McElroy, 1983;Heinze et al., 1991;Falkowski, 1997).
On a global scale the C : N : P ratios of dissolved carbon and nutrients in the ocean are remarkably consistent with the traditional Redfield ratio of C : N : P = 106 : 16 : 1 for the photosynthetic production of organic matter (Redfield et al., 1963;Takahashi et al., 1985;Anderson and Sarmiento, 1994).Nevertheless on a more regional scale a pronounced variability of C : N : P ratios exists.The C : N : P ratio of phytoplankton shows sensitivity to nutrient availability, growth rate, taxonomy and ambient CO 2 concentrations (Arrigo, 2005;Riebesell et al., 2007).
Eastern boundary upwelling systems (EBUS) are regions of high CO 2 concentrations (Boehme et al., 1998;Torres et al., 1999) and intense biological production and export of carbon (Carr, 2002).They as well play an important role in supplying nutrients to the surface mixed layer of adjacent oligotrophic subtropical gyres where nutrient supply is limited by stable thermal stratification (Behrenfeld et al., 2006a).The Benguela upwelling system (BUS) is a coastal upwelling system known for non-standard nutrient (N : P) ratios in upwelling waters (Tyrrell and Lucas, 2002) caused by N reduction (anammox and/or denitrification) and P release from sediments in low O 2 environments (Kuypers et al., 2005;Nagel et al., 2013).The C : N : P remineralization ratios in the Introduction

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Full subsurface waters are poorly constrained but are crucial in order to characterize the cycling of C in the BUS.We analyzed nutrient (NO − 3 , NO − 2 , P) and dissolved O 2 data in conjunction with data on dissolved inorganic carbon (C T ) and alkalinity (A T ) raised during an expedition in 2011, and complemented these with nutrient data from 2 other expeditions staged in 2008 and 2009.Our objectives were to identify the spatial variability of the C : N : P : O 2 mineralization ratios of the northern BUS (NBUS), to study the spatial and temporal variability of biogeochemical conditions influencing the N losses, and associated consequences for the nutrient export from the eutrophic upwelling system into the oligotrophic subtropical gyre.

Study area
The BUS spans along the south western coast of Africa, covering the western South African and Namibian coastline roughly from Cape Agulhas (∼ 34 • S) to the Angola Benguela Frontal Zone (ABFZ) (Hutchings et al., 2009) (Fig. 1a).At the ABFZ, which is centred between 14 • S and 16 • S (Meeuwis and Lutjeharms, 1990) but is highly dynamic in terms of shape and location, the cold Benguela current system converges with warm tropical waters of the surface Angola Current (AC).To the south, the system is bordered by the Agulhas Current that reverses and partly converges with the South Atlantic water resulting in the formation of eddies (Agulhas Rings, AR) and filaments (Hall and Lutjeharms, 2011).
Along the coast of SW Africa, the interaction of southerly trade winds with coastal topography forces upwelling, which is strongest at 3 distinct upwelling cells (Shillington et al., 2006;Hutchings et al., 2009).The Lüderitz upwelling cell (∼ 26 • S) accounts for roughly 50 % of physical upwelling and separates the upwelling region into a northern and a southern subsystem (Shannon, 1985;Duncombe Rae, 2005).In the southern Introduction

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Full region (south of 26 • S) the trade winds are seasonal and upwelling has maxima during austral spring and summer.The northern region (from 26 • S to the ABFZ) is characterized by perennial alongshore winds and upwelling along the coast (Shannon, 1985).The Lüderitz cell also marks the boundary of two intermediate water regimes that cause distinct differences in biogeochemical properties of upwelling waters.Upwelling in the southern BUS entrains Eastern South Atlantic Water (ESACW) into the offshore Ekman drift at the surface (Duncombe Rae, 2005;Mohrholz et al., 2007).The ESACW is an intermediate water mass formed at the Brazil-Falkland confluence off South America (Gordon, 1981;Stramma and England, 1999) and flows along with the southern branch of the Subtropical Gyre and the Benguela Current northwards into the NBUS (Gordon, 1981;Sprintall and Tomczak, 1993;Poole and Tomczak, 1999).
Here, the ESACW mixes with an Angola Gyre subtype of the South Atlantic Central Water (SACW).The SACW originates in the subtropical Angola Gyre and forms a poleward undercurrent flowing along the continental margin and the Namibian shelf break (Duncombe Rae, 2005;Mohrholz et al., 2007).The SACW is originally a branch of ESACW that penetrated further northward into the equatorial system of intermediate water masses.It is older than the ESACW and thus enriched in CO 2 and nutrients, and depleted in O 2 .Increased inflow of SACW into the NBUS preconditions the development of an oxygen minimum zone (OMZ) and anoxic events over the Namibian shelf and upper slope (Weeks et al., 2002;Monteiro et al., 2006;Mohrholz et al., 2007).
On the shelf at low O 2 concentrations (< 20 µM O 2 ) NO x is reduced by denitrification and/or anammox (Lam and Kuypers, 2010;Kalvelage et al., 2011).The loss of fixed N to anammox within the OMZ on the shelf has been estimated to ∼ 1.4 Tg N a −1 (Kuypers et al., 2005) and the loss to denitrification to ∼ 2.5 Tg N a −1 (Nagel et al., 2013).However, N loss exceeds estimates on N 2 fixation (Sohm et al., 2011) suggesting that the BUS acts as net sink for fixed N. Furthermore, the BUS shelf is a region of modern phosphorite deposition (Glenn et al., 1994;Föllmi, 1996) associated with a massive organic rich diatomaceous mud belt that roughly follows the Namibian coast between 50 and 200 m water depth and covers an area of ∼ 18 000 km 2 (Bremner, Introduction

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Water sampling and analysis
Nutrient samples were collected during three cruises in austral summer and early autumn (Fig. 1b): MSM07/2b-3 (RV Maria S. Merian, 9 March-17 April 2008) Rocky Point and Walvis Bay where sampled during all of the three cruises.Samples were collected by CTD casts using a rosette system equipped with 10 L Niskin bottles.
The analyzed parameters presented in this study comprise dissolved inorganic carbon (C T ), total alkalinity (A T ) and dissolved nutrients (NO x = nitrate (NO 2 ) and phosphate (PO 3− 4 )).

C T and A T
The C T and A T samples were taken during the MSM17/3 cruise.Transects off Kunene (17.25 • S), Rocky Point (19.00 • S), Terrace Bay (20.00 • S), Toscanini (20.80 • S) and Walvis Bay (23.00 • S) were sampled.For C T and A T analysis the samples were filled in 250 mL borosilicate bottles using silicone tubes (Tygon).The bottles were rinsed twice and filled from the bottom to avoid bubbles.Periodically duplicate samples were taken.The samples were fixed with mercuric chloride solution (250 µL of a 35 g L −1 HgCl 2 ) directly after collection and analyzed on board using the VINDTA 3C system (Marianda, Introduction

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Full Kiel, Germany).The A T was determined on the basis of the open cell principle.The samples were titrated with a fixed volume of hydrochloric acid by equal increments of HCl (0.1 N HCl).For the determination of C T , the CO 2 was extracted out of acidified water samples and quantified by the coulorimetric method with a precision of 0.1 %.Certified Reference Material (CRM, batch #101 and #104, provided by A. Dickson (Scripps Institution of Oceanography, La Jolla, CA, USA)) was used to calibrate the VINDTA 3C system.The C T and A T measurements of duplicate samples agreed to ±2 µmol kg −1 .In the following A T is reported as the salinity corrected value (A T = A Tmeas × 35/S meas ).

Dissolved nutrients
The nutrient samples were filtered through disposable syringe filters (0.45 µm) immediately after sampling, filled in pre-rinsed 50 mL PE bottles and frozen (−20 • C).Samples collected during the MSM07/2b-3 cruise were measured on board, whereas samples taken during Afr258 and MSM17/3 cruises were analyzed in the shore-based laboratory subsequently to the expedition.Dissolved nutrients were measured by a continuous flow injection system (Skalar SAN plus System) according to methods described by Grasshoff et al. (1999).The detection limits were: NO x = 0.08 µM and PO 3 4 = 0.07 µM according to DIN 32645.Ammonium (NH + 4 ) concentrations were usually < 2.5 µmol kg −1 and are not discussed in this paper.

Characterization of SACW and ESACW
The potential temperature (T pot ) and salinity characteristics were used to differentiate between SACW and ESACW contributions.Their definitions were adopted from Mohrholz et al. (2007), who identified an Angola Gyre subtype of SACW.The ESACW and SACW are defined by a line in T pot -Salinity (S) space that can be described by Introduction

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Full the following equations: (1) The above equations were transformed to calculate the respective proportions of SACW and ESACW: S ESACW = (T pot + 319.03)/9.4454(4) The relative contribution of SACW and ESACW are reported in percentage [%].Data derived from water depths < 100 m were excluded from this mixing analysis due to the non-conservative behaviour of T pot and S at shallower water depths.

Anomalies of N : P stoichiometry
To calculate the deviation from the classical Redfield ratio (N : P = 16 : 1) (Redfield et al., 1963) we used the tracer N * (Gruber and Sarmiento, 1997): Positive and negative N * imply a relative excess or deficit of nitrate and nitrite (N) relative to phosphate (P), respectively, whereas N * = 0 represents the global mean value that has an N deficit of −2.9 µmol kg −1 at 0 µmol kg

Results and discussion
It has been shown that on a global scale the distribution of N : P is characterized by a relative deficit of N towards P. The intercept of global N : P nutrient data indicate a P excess of ∼ 0.18 µmol kg −1 in the global surface ocean (Gruber and Sarmiento, 1997) and the mean slope is with N : P = 14-15 : 1 below the classical Redfield correlation of N : P = 16 : 1 (Redfield et al., 1963) due to a net loss of fixed N that, as mentioned before, occurs e.g.within the OMZ on the Namibian shelf (Kuypers et al., 2005;Nagel et al., 2013).In the following the C : N : P remineralization patterns observed in 2011 are discussed with regard to their spatial variability and are complemented by results on the temporal variability of N : P anomalies recorded in 2008 and 2009.

C : N : P : AOU stoichiometry
The NO x and PO 3− 4 concentrations from the NBUS scattered to both sides of the reference Redfield slope and characterize the NBUS as a system that produces both positive and negative deviations from Redfield expressed in positive and negative N * anomalies (Fig. 2).Major negative anomalies were apparent at shelf sites.Tyrrell and Lucas (2002) attributed low N : P (LNP) data (N : P < 3 and PO 3− 4 > 1.5 µmol kg −1 ) in waters of the BUS to nutrient trapping and denitrification that leads to a relative accumulation of P. Figure 3  4 ratio of 101 : 1 that is similar to the global mean C : P ratio of 106 : 1 (Redfield et al., 1963;Anderson and Sarmiento, 1994).The C T : PO of sulphur bacteria (Schulz and Schulz, 2005).This in line with previous hypotheses that the stoichiometric N deficit in waters over the Namibian shelf is, next to the impact of NO x reduction, in part caused by P fluxes across the sediment water interface (Bailey and Chapman, 1991;Nagel et al., 2013).The impact of NO x loss and benthic fluxes of PO

Spatial and temporal variability
Inter-annual differences in upwelling conditions during austral summer expeditions were well reflected in the distribution of sea surface temperatures (SST).Weak upwelling phases, such as that in February 2011 permit SACW to protrude far southward (Fig. 7d-f).In this situation, this water mass accounted for 70 % of the subsurface water off Walvis Bay ( 23• S) during weak upwelling.The dominance of SACW was reflected in mid-water O 2 deficits, so that samples with ≥ 80 % SACW were associated with ≤ 50 µmol kg −1 O 2 (Fig. 7a-c).During strong and weak upwelling alike and regardless of the SACW contribution, the O 2 concentrations on the shelf off Walvis Bay were < 20 µmol kg −1 during all cruises.The contribution of SACW thus sets the precondition for anoxia in bottom waters off Walvis Bay (Monteiro et al., 2008), but O 2 consumption caused by the decomposition of organic matter exported from the surface plays a decisive role (Monteiro et al., 2006;van der Plas et al., 2007).
The N : P deviation from Redfield (as indicated by N * ) varied during the different expeditions and upwelling states (Fig. 8).This variability was not apparently tied to the distribution of SACW and O 2 concentrations at offshore sites (Fig. 7a-c).From the temporal variability in patterns of N * in the hemipelagic OMZ offshore of Kunene (17.25 • S) it is apparent that N * in the SACW water mass varied significantly between years (Fig. 9).During March 2008 (MSM07/2b-3), N * was 3 fold increased within the

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Full March 2008 by a factor of > 2. The results suggest that the considerable variability in nutrient ratios of SACW controls the inter-annual variability of N * in the NBUS.Positive N * anomalies in subsurface waters are commonly attributed to the mineralization of organic matter produced by N 2 -fixing organisms (Gruber and Sarmiento, 1997) that have N : P ratios of up to 150 (Krauk et al., 2006).Positive N * anomalies in the tropical and subtropical North Atlantic are ∼ 4 µmol kg −1 at σ θ = 26.5 (Gruber and Sarmiento, 1997;Mahaffey et al., 2005).Here, intensive blooms of Trichodesmium spp.(Carpenter, 1983;Tyrrell et al., 2003;Capone et al., 2005) and high N : P (of up to 35) have been reported (Mahaffey et al., 2003) and are consistent with N 2 fixation as a significant input source, which can raise N * to ∼ 20 µmol kg −1 (Mahaffey et al., 2003).In contrast, the South Atlantic gyre has low positive N * (Gruber and Sarmiento, 1997), in line with low rates of N 2 fixation (Mahaffey et al., 2005) that has been attributed to a lack of iron (Fe) supply (Moore et al., 2009).However, Sohm et al. (2011) observed N 2 fixation within the ABFZ (∼ 13-15 • S) coincident with decreased thermocline δ 15 N − NO 3 values and elevated dissolved Fe and cobalt surface concentrations (Noble et al., 2012) that are important micronutrients for marine diazotrophic cyanobacteria (Saito et al., 2002(Saito et al., , 2004)).The studies of Sohm et al. (2011) and Noble et al. (2012) were performed in November-December 2007 and hence ∼ 4 months prior to the MSM07/2b-3 expedition in March 2008 that found the positive N * anomaly in SACW.Although the N 2 fixation rates measured by Sohm et al. (2011) were relatively low (22-85 µmol N m −2 d −1 ), N 2 fixation north of the ABFZ is the only feasible input source that caused the observed high N excess in the SACW in 2008.

NBUS -a P * -source for the South Atlantic
Upwelling of N-deficient water in 2009 and 2011 caused lowest N * at 5 m depth close to the coast (Fig. 8d-f) indicating that a relative P surplus surfaces and is advected offshore into the open ocean with modified upwelling water.This should stimulate N 2 fixation in the adjacent hemipelagic ocean (Deutsch et al., 2007), but experimentally Introduction

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Full determined rates of N 2 fixation in the NBUS and its periphery were very low to not detectable (N. Wasmund, personal communication, 2012).We calculated the P excess (P * ) within the euphotic zone (0-20 m) that is exported offshore for the Walvis Bay (23 • S) transect (Fig. 10).Roughly 300 km offshore, beyond the continental slope, P * was close to zero in March 2008 (P * = 0.007 ± 0.09 µmol kg −1 ), suggesting that the NBUS at that time was not a regional P source for the oligotrophic subtropical South Atlantic.During the other cruises, the NBUS was a relative P source with P * values of 0.3 ± 0.01 µmol kg −1 .These observations are in line with Staal et al. (2007) and Moore et al. (2009) who reported surface P * = 0.15-0.30µmol kg −1 within areas of the Subtropical Gyre that are influenced by the advection of water masses transported by the Benguela Current.Along with our findings, it implies that the coastal upwelling system over the shelf is a P * source to the South Atlantic most of the time.Since the mud belt is a geological feature and the O 2 concentration off Walvis Bay was < 20 µmol kg −1 independently from the upwelling situation (Fig. 7a-c) it is assumed that the inter-annual variability of that P source depends mainly on the N excess in the SACW that is produced probably by N 2 fixation north of the ABFZ.We further presume that N 2 fixation in this region is in turn linked to the NBUS by the export of P * into the South Atlantic ocean and its advection along with the major surface currents to the Angola Gyre and ABFZ region (Fig. 11).

Conclusions
Our which the N loss on the shelf is balanced by enhanced N inputs along with the SACW controls the amount of P * that is exported from the NBUS into the subtropical South Atlantic.To better understand the NBUS' role in the coupled C : N : P cycles and its response to global change, factors controlling e.g. the occurrence of N 2 fixation at the ABFZ need to be addressed in future studies.

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Full Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | −1 P (or a P excess of 0.18 µmol kg −1 ).For better comparability with literature we use the concept of Deutsch et al. (2007) to quantify the P anomaly (P * ) from Redfield: P * = [PO 3Discussion Paper | Discussion Paper | Discussion Paper | illustrates the relationships between apparent oxygen utilization (AOU) calculated from O 2 concentrations, NO x (NO C T of the water samples in 2011 (MSM17/3).The observed average C T : AOU ratio of 0.76 (r 2 = 0.89) is close to that expected from a mineralization C:O 2 ratio of 106 : −138 (Fig. 3a).Exclusion of the O 2 < 20 µmol kg −1 data gave no mentionable differences between the shelf (C T : AOU = 0.77, r 2 = 0.88) and offshore sites (C T : AOU = 0.75, r 2 = 0.89).The scattering of data in Fig. 3a is likely due to the fact that the shelf system is not truly closed and that O 2 is introduced into the subsurface water masses on the shelf through Discussion Paper | Discussion Paper | Discussion Paper |O 2 < 20 µmol kg −1 implies C T input from anerobic respiration, such as denitrification and is evident from decreasing NO x associated with increasing C T concentrations at O 2 < 20 µmol kg −1 (Fig.3b).At higher O 2 the overall average C T : NO x = 6.1 (r 2 = 0.86) is similar to the Redfield ratio of 6.6 with slightly lower values in the open ocean (5.5, r 2 = 0.89) than on the shelf (6.8, r 2 = 0.86).The slope of the A T : C T ∼ −0.15 (Fig.4) observed in the paired data agrees with the expected effect of aerobic organic matter remineralization (A T : C T = −16 : 106) ratio due to the release of CO 2 and NO − 3 (Broecker and Peng, 1982) and imply that carbonate dissolution hardly affected the C T and the A T concentrations.At O 2 concentrations < 20 µmol kg −1 , both anammox and denitrification increase A T through the consumption of NO x .However, a decrease in C T indicating a dominance of anammox over heterotrophic denitrification is not visible in our data (Fig. 3b) likely due to the low C : N stoichiometry of anammox (C : N ∼ −0.07 : −1.3) compared to that of denitrification (C : N ∼ 106 : −104) (Koeve and Kähler, 2010).A loss of NO x by 20 µmol kg −1 would result in a C T decrease of −1 µmol kg −1 due to anammox and a C T increase of +21 µmol kg −1 during denitrification.A source for PO 3− 4 besides mineralization of organic matter in the water column is suggested by the spread of C T : PO 3− 4 data in Fig. 3c.Open ocean sites had an average C T : PO 3− splits in 2 groups.One group revealed a slope of the regression line of ∼ 98 : 1 (r 2 = 0.82) which is similar to those seen in the offshore samples.The remaining samples suggest a much lower average C T : PO 3− 4 ratio of ∼ 65 (r 2 = 0.84) and are related to the mud belt region off Walvis Bay.Even lower C : P ratios of 48-33 were measured in pore waters near the sediment water interface within the mud belt(Goldhammer et al., 2011).Because PO 3− 4 concentrations higher than expected from mineralization of organic matter occurred exclusively at shelf sites the low C T : PO 3− 4 imply an impact of pore water P-effluxes from anoxic sediments mediated by consortia Discussion Paper | Discussion Paper | Discussion Paper | Namibian shelf and slope (Fig.5; exemplary for the MSM17/3 cruise in February 2011).The mid-water OMZ off Kunene (17.25 • S) disappeared towards the south and instead the OMZ was restricted to the shelf off 23 • S. Pore water effluxes at low O 2 concentrations shifted as well, so that off 23• S).Due to N losses at low O 2 concentrations, the NO x maxima were observed outside the OMZ and decreased from 45 µmol kg −1 (17.25•S) to 35 µmol kg−1 (23 • S).Although the N loss likely contributes to the overall NO x decrease, it also reflects the gradual increase of ESACW fraction towards the south.This water mass is characterized by lower nutrient concentrations than SACW(Poole and Tomczak, 1999;Mohrholz et al., 2007).Concluding, C : N : P : O 2 ratios at offshore sites are 101 : 16 : 1 : 138 and are stoichiometrically close to Redfield ratios, whereas PO 3− 4 input lowers the C : N : P : O 2 ratio to 106 : 16 : 1.6 : 138 over the shelf off Walvis Bay.Only in regions with O 2 concentrations < 20 µmol kg −1 , denitrification increases C : N and denitrification and anammox further lower N : P ratios.
The SST patterns, measured continuously by thermo-salinographs at 5 m water depth, indicate that upwelling was most intense in December 2009 (Afr258) (Fig. 6), when minimum SST (15 • C) occurred along the entire coast and temperatures < 20 • C were measured Discussion Paper | Discussion Paper | Discussion Paper |far offshore.In contrast, most of the NBUS had SST > 20 • C during February 2011 (MSM17/3).In March 2008 (MSM07/2b-3) SST outline an intermediate upwelling intensity in a coastal band of low temperatures.Stronger or weaker upwelling is associated with distinct distributions of the central water masses on the shelf.Mohrholz et al. (2007) found that vigorous cross shelf circulation during phases of strong upwelling suppresses the along-shelf pole-ward undercurrent of SACW from the north.
Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | Discussion Paper | data measured during the cruise in March 2011 show a mean C : N : P : O 2 ratio that is close to the Redfield stoichiometry.Over the mud belt on the Namibian shelf pore water fluxes lowered the C : N : P : O 2 ratio to 106 : 16 : 1.6 : 138.Only in restricted regions were O 2 concentration dropped below 20 µmol kg −1 , N losses further increased the C : N and reduced N : P ratios.Additional nutrient data measured during 2 cruises in 2008 and 2009 reveal an inter-annual variability of N excess within the SACW that flows from the north into the NBUS with highest N * values observed in 2008.The degree to Discussion Paper | Discussion Paper | Discussion Paper |