Eastern Tropical South Pacific Research Articles

Dissolved Organic Nitrogen Production and Consumption in Eastern Tropical South Pacific Surface Waters

AbstractModels of dissolved organic nitrogen (DON) production and consumption indicate that marine DON is produced in the euphotic zone, especially in upwelling environments, and is consumed as it transits into more oligotrophic regions where it may support export production. However, evaluation of such models is data limited, and in particular, few measurements of DON concentration and/or nitrogen isotopic composition (“δ15N”) exist from the South Pacific. Here we present measurements of the concentration and δ15N of DON collected in the eastern tropical South Pacific during the austral summers of 2010 (El Niño) and 2011 (La Niña). The concentration and δ15N of DON from the eastern tropical South Pacific are broadly consistent with prior measurements elsewhere, that is, DON concentrations of 5 ± 1 μM and DON δ15N of 5 ± 1‰, but variations were associated with DON production and consumption. Specifically, surface ocean chlorophyll a concentrations were highly correlated with upper 50‐m DON stocks (r = 0.96), consistent with a photosynthetic source for DON. Additionally, upper 50‐m DON stocks and their δ15N were significantly negatively correlated (r = −0.84, p = 0.0006), indicating that DON was consumed in surface waters with an isotope effect of 5.5 ± 1.2‰. These results inform our understanding of the controls of DON distributions in the surface ocean and indicate that DON may support export production in nitrate‐poor surface waters, which may decouple new from gross production.

Metabolic potential and in situ transcriptomic profiles of previously uncharacterized key microbial groups involved in coupled carbon, nitrogen and sulfur cycling in anoxic marine zones.

Anoxic marine zones (AMZs) impact biogeochemical cycles at the global scale, particularly the nitrogen cycle. Key microbial players from AMZs have been identified, but the majority remains unrecognized or uncharacterized. Thirty-one single-cell amplified genomes (SAGs) from the eastern tropical North and South Pacific AMZs were sequenced to gain insight into the distribution, metabolic potential and contribution to the community transcriptional profile of these uncharacterized bacterial and archaeal groups. Detailed analyses focused on SAG-bins assigned to three of these groups that presented 79%-100% estimated genome completeness: the putative sulphur-oxidizing Gamaproteobacteria EOSA II clade, a Marinimicrobia member of the recently recognized PN262000N21 clade found to be abundant in AMZ anoxic cores, and a representative of the Marine Benthic Group A Thaumarchaeota. Community-based analyses revealed that these three groups are significantly more abundant and transcriptionally more active in the AMZ microbial communities than previously described phylogenetically related microbial groups. Collectively, these groups have the potential to link biogeochemically relevant processes by coupling the carbon, nitrogen and sulfur cycles. Together, these results increase our understanding of key microbial components inhabiting AMZs and other oxygen-deficient marine environments, enhancing our capacity to predict the impact of the expansion of these ecosystems due to climate change.

Glacial–interglacial changes and Holocene variations in Arabian Sea denitrification

Abstract. At present, the Arabian Sea has a permanent oxygen minimum zone (OMZ) at water depths between about 100 and 1200 m. Active denitrification in the upper part of the OMZ is recorded by enhanced δ15N values in the sediments. Sediment cores show a δ15N increase during the middle and late Holocene, which is contrary to the trend in the other two regions of water column denitrification in the eastern tropical North and South Pacific. We calculated composite sea surface temperature (SST) and δ15N ratios in time slices of 1000 years of the last 25 kyr to better understand the reasons for the establishment of the Arabian Sea OMZ and its response to changes in the Asian monsoon system. Low δ15N values of 4–7 ‰ during the last glacial maximum (LGM) and stadials (Younger Dryas and Heinrich events) suggest that denitrification was inactive or weak during Pleistocene cold phases, while warm interstadials (ISs) had elevated δ15N. Fast changes in upwelling intensities and OMZ ventilation from the Antarctic were responsible for these strong millennial-scale variations during the glacial. During the entire Holocene δ15N values > 6 ‰ indicate a relatively stable OMZ with enhanced denitrification. The OMZ develops parallel to the strengthening of the SW monsoon and monsoonal upwelling after the LGM. Despite the relatively stable climatic conditions of the Holocene, the δ15N records show regionally different trends in the Arabian Sea. In the upwelling areas in the western part of the basin, δ15N values are lower during the mid-Holocene (4.2–8.2 ka BP) compared to the late Holocene (< 4.2 ka BP) due to stronger ventilation of the OMZ during the period of the most intense southwest monsoonal upwelling. In contrast, δ15N values in the northern and eastern Arabian Sea rose during the last 8 kyr. The displacement of the core of the OMZ from the region of maximum productivity in the western Arabian Sea to its present position in the northeast was established during the middle and late Holocene. This was probably caused by (i) reduced ventilation due to a longer residence time of OMZ waters and (ii) augmented by rising oxygen consumption due to enhanced northeast-monsoon-driven biological productivity. This concurs with the results of the Kiel Climate Model, which show an increase in OMZ volume during the last 9 kyr related to the increasing age of the OMZ water mass.

Cyanate distribution and uptake above and within the Eastern Tropical South Pacific oxygen deficient zone

AbstractCyanate is a simple reduced nitrogen (N) compound that can be a source of N and carbon (C) for marine organisms and may also be a substrate for dissimilatory N processes such as nitrification and anammox. We measured cyanate distributions and cyanate and urea uptake in the Eastern Tropical South Pacific, a region defined by coastal upwelling, high primary productivity, a shallow oxic layer, and rapid N loss from a large oxygen deficient zone (ODZ). Cyanate concentrations ranged from below the limit of detection (0.4 nM) to 45 nM in the oxic upper water column. Below the oxycline, cyanate concentrations were largely below detection except for small cyanate peaks (2–8.3 nM) within the core of the ODZ at some stations. The majority of N taken up in the shallow oxic layer was from ammonium and urea (78% ± 8%); cyanate uptake was < 2% of these. Uptake of cyanate fluctuated diurnally with the highest rates of cyanate N uptake in the early afternoon. In the ODZ, rates of cyanate, urea, and ammonium uptake were similar to each other (0.1–14 nmol N L−1 d−1) and to previously reported rates of 29N2 production supported by cyanate and ammonium (3–14 nmol N2 L−1 d−1). This suggests a role for cyanate in the metabolism of anaerobic microbes and a potential role for cyanate in the anammox reaction (cyanammox). To our knowledge, these represent the first rates of N uptake in a marine anoxic water column.

234Th as a tracer of particulate export and remineralization in the southeastern tropical Pacific

Abstract Oxygen minimum zones (OMZs) are thought to be regions of decreased carbon attenuation in the upper ocean with a biological pump that could deliver a greater percentage of exported carbon to the mesopelagic relative to surrounding waters. However, much is still unknown about carbon cycling through these zones and the areas of extreme oxygen minima (nM O 2 ) or oxygen deficient zones (ODZs) within the OMZs. Paired sampling for 234 Th (t½ ~ 24.1 days) and particulate organic carbon (POC) was performed along a zonal transect between 77 and 152°W during the U.S. GEOTRACES Southeastern Tropical Pacific campaign in 2013 in order to constrain the magnitude of carbon export and remineralization through the Peruvian OMZ. POC export varied by an order of magnitude from the coast to 152°W, reflecting a decrease in POC: 234 Th ratios (> 51 μm) with distance offshore and the influence of upwelling at the coast. Modeling indicated that 234 Th fluxes could be underestimated at coastal stations by up to 4-fold without adjustment for the impact of upwelling, which in turn would produce much lower carbon export estimates. Low carbon Export:NPP ratios ( 7500 km that resulted in, on average, 3% of the POC exported from the euphotic zone reaching 100 m below the Ez. Although the highest percentages (> 10%) of total exported POC at 100 m below the Ez were observed in the coastal ODZ region, the observed remineralization was also most pronounced these stations. While an average of 75% of the carbon export from the euphotic zone remained at Ez + 100 m in the gyre, a range of 10 to 50% was observed at ODZ stations, reflecting increased attenuation. Local subsurface minima in light transmission and maxima in fluorescence were observed in the regions of greatest remineralization at the upper ODZ boundary, suggesting that complex bacterial community dynamics play a role in increased attenuation through these zones. With ODZs and OMZs predicted to grow worldwide with climate change, these areas require further large-scale and seasonal studies to assess the permanency of these attenuation features and the impact of high Gyre and lower ODZ transfer of POC on the overall efficiency of carbon export in the Pacific.

Community Composition of Nitrous Oxide Consuming Bacteria in the Oxygen Minimum Zone of the Eastern Tropical South Pacific.

The ozone-depleting and greenhouse gas, nitrous oxide (N2O), is mainly consumed by the microbially mediated anaerobic process, denitrification. N2O consumption is the last step in canonical denitrification, and is also the least O2 tolerant step. Community composition of total and active N2O consuming bacteria was analyzed based on total (DNA) and transcriptionally active (RNA) nitrous oxide reductase (nosZ) genes using a functional gene microarray. The total and active nosZ communities were dominated by a limited number of nosZ archetypes, affiliated with bacteria from marine, soil and marsh environments. In addition to nosZ genes related to those of known marine denitrifiers, atypical nosZ genes, related to those of soil bacteria that do not possess a complete denitrification pathway, were also detected, especially in surface waters. The community composition of the total nosZ assemblage was significantly different from the active assemblage. The community composition of the total nosZ assemblage was significantly different between coastal and off-shore stations. The low oxygen assemblages from both stations were similar to each other, while the higher oxygen assemblages were more variable. Community composition of the active nosZ assemblage was also significantly different between stations, and varied with N2O concentration but not O2. Notably, nosZ assemblages were not only present but also active in oxygenated seawater: the abundance of total and active nosZ bacteria from oxygenated surface water (indicated by nosZ gene copy number) was similar to or even larger than in anoxic waters, implying the potential for N2O consumption even in the oxygenated surface water.

Biogeochemical cycling of Fe and Fe stable isotopes in the Eastern Tropical South Pacific

The basin-scale distributions of iron (Fe) and Fe isotopes provide important insights into the biogeochemical cycling of this growth-limiting micronutrient in the ocean. Here we present new observations of dissolved Fe concentrations and stable isotope ratios (δ56Fe) from the US GEOTRACES Eastern Pacific Zonal Transect GP16. The western portion of the transect is characterized by low dissolved Fe concentrations with a heavy δ56Fe signature of + 0.4 to + 0.6‰, similar to the dust-influenced North Atlantic deep waters. This is punctuated by Fe inputs from hydrothermal vents along the East Pacific Rise, with a δ56Fe of − 0.3‰. One striking feature of the transect is a large plume of high dissolved Fe and low δ56Fe (0 to − 0.5‰) in the east, near the Peru margin. Here, maximum dissolved Fe occurs between 1000 and 3000 m and the elevated concentrations persist over 1000 km from the margin. The region of markedly lower δ56Fe extends even further, to roughly 4000 km offshore. The mid-slope depth at which this plume occurs (1000–3000 m) is at odds with current conceptual and numerical models of Fe inputs along continental margins, which predict a shallower and more restricted dissolved Fe maximum (upper-slope; ~ 100–1000 m). Here, we explore four possible explanations for the mid-slope Fe plume: (1) Fe fluxes are actually higher from mid-slope sediments; (2) the mid-slope plume is transported from a remote region (3) mid-slope Fe originates from resuspended sediments in a very persistent form, which remains in the dissolved phase for longer than Fe released from the upper-slope; (4) Fe is supplied from upper-slope sediments, and then transferred to greater depth by reversible scavenging onto sinking particles. Simple modeling is used to show that both input of persistent Fe from mid-slope sediments and reversible scavenging could explain the data. Flux of a more persistent chemical form of Fe from the mid-slope would be consistent with other tracers such as particle composition and 228Ra, which suggest that lithogenic sediments are preferentially resuspended at this depth, but may be at odds with the low δ56Fe signature. Reversible scavenging is consistent with both Fe concentrations and δ56Fe. Whatever its provenance, the plume observed near the Peru margin impacts Fe concentrations and δ56Fe throughout the entire eastern South Pacific region, suggesting that the roles of persistent Fe input and reversible scavenging should be appraised in fully coupled iron-carbon cycle models in order to better understand the global cycling of Fe and δ56Fe.

Biogeochemical cycling of Zn and Cd and their stable isotopes in the Eastern Tropical South Pacific

Abstract The distribution of Zn and Cd and their stable isotope ratios (δ66Zn and δ114Cd) were measured on samples from the Eastern Subtropical South Pacific Zonal Transect (EPZT), US GEOTRACES section GP16. The broad trends in both δ66Zn and δ114Cd are similar to those observed in other ocean basins, suggesting global similarities in the biogeochemical processes which cycle Zn and Cd. For example, average deep ocean δ66Zn along this transect (+ 0.46‰) are similar to the ~+0.5‰ values observed in the deep North Atlantic and North Pacific. Also similar to other locations, δ66Zn decreases towards the surface ocean. A plume of hydrothermal Zn emanating from the East Pacific Rise is used to calculate hydrothermal end-member δ66Zn as + 0.24‰, which is similar to crustal values and similar to other sources of Zn to the oceans. Average deep-ocean δ114Cd along this transect is + 0.28‰, which is similar to deep-ocean values between + 0.2 and + 0.3 measured elsewhere in the Atlantic, Pacific, and Southern Oceans. δ114Cd increases towards the surface ocean, as observed in other ocean basins, reflecting the preferential biological uptake of lighter Cd isotopes. Elsewhere it has been hypothesized that Cd can precipitate in sulfidic microenvironments on sinking particles, affecting seawater Cd concentrations and isotope ratios. However, we don't find evidence of particularly strong CdS precipitation along this transect, despite the fact that the Peru OMZ is one of the most reducing ocean environments worldwide.

A Review of Protist Grazing Below the Photic Zone Emphasizing Studies of Oxygen-Depleted Water Columns and Recent Applications of In situ Approaches

Little is still known of the impacts of protist grazing on bacterioplankton communities in the dark ocean. Furthermore, the accuracy of assessments of in situ microbial activities, including protist grazing, can be affected by sampling artifacts introduced during sample retrieval and downstream manipulations. Potential artifacts may be increased when working with deep-sea samples or samples from chemically unique water columns such as oxygen minimum zones (OMZs). OMZs are oxygen-depleted regions in the ocean, where oxygen concentrations can drop to <20 µM. These regions are typically located near eastern boundary upwelling systems and currently occur in waters occupying below about 8% of total ocean surface area, representing ~1% of the ocean’s volume. OMZs have a profound impact not only on the distribution of marine Metazoa, but also on the composition and activities of microbial communities at the base of marine food webs. Here we present an overview of current knowledge of protist phagotrophy below the photic zone, emphasizing studies of oxygen-depleted waters and presenting results of the first attempt to implement new technology for conducting these incubation studies completely in situ (the Microbial Sampling- Submersible Incubation Device, MS-SID). We performed 24-h incubation experiments in the Eastern Tropical South Pacific (ETSP) OMZ. This preliminary study shows that up to 28% of bacterial biomass may be consumed by protists in waters where oxygen concentrations were down to ~3 µM and up to 13% of saturation at a station with nitrate accumulation where oxygen concentrations were undetectable. Results also show that shipboard measurements of grazing rates were lower than rates measured from the same water using the MS-SID, suggesting that in situ experiments help to minimize artifacts that may be introduced when conducting incubation studies using waters collected from below the photic zone, particularly from oxygen-depleted regions of the water column.

Multiple metabolisms constrain the anaerobic nitrite budget in the Eastern Tropical South Pacific

AbstractThe Eastern Tropical South Pacific is one of the three major oxygen deficient zones (ODZs) in the global ocean and is responsible for approximately one third of marine water column nitrogen loss. It is the best studied of the ODZs and, like the others, features a broad nitrite maximum across the low oxygen layer. How the microbial processes that produce and consume nitrite in anoxic waters interact to sustain this feature is unknown. Here we used 15N‐tracer experiments to disentangle five of the biologically mediated processes that control the nitrite pool, including a high‐resolution profile of nitrogen loss rates. Nitrate reduction to nitrite likely depended on organic matter fluxes, but the organic matter did not drive detectable rates of denitrification to N2. However, multiple lines of evidence show that denitrification is important in shaping the biogeochemistry of this ODZ. Significant rates of anaerobic nitrite oxidation at the ODZ boundaries were also measured. Iodate was a potential oxidant that could support part of this nitrite consumption pathway. We additionally observed N2 production from labeled cyanate and postulate that anammox bacteria have the ability to harness cyanate as another form of reduced nitrogen rather than relying solely on ammonification of complex organic matter. The balance of the five anaerobic rates measured—anammox, denitrification, nitrate reduction, nitrite oxidation, and dissimilatory nitrite reduction to ammonium—is sufficient to reproduce broadly the observed nitrite and nitrate profiles in a simple one‐dimensional model but requires an additional source of reduced nitrogen to the deeper ODZ to avoid ammonium overconsumption.

Enhanced Nitrogen Loss by Eddy-Induced Vertical Transport in the Offshore Peruvian Oxygen Minimum Zone.

The eastern tropical South Pacific (ETSP) upwelling region is one of the ocean’s largest sinks of fixed nitrogen, which is lost as N2 via the anaerobic processes of anammox and denitrification. One-third of nitrogen loss occurs in productive shelf waters stimulated by organic matter export as a result of eastern boundary upwelling. Offshore, nitrogen loss rates are lower, but due to its sheer size this area accounts for ~70% of ETSP nitrogen loss. How nitrogen loss and primary production are regulated in the offshore ETSP region where coastal upwelling is less influential remains unclear. Mesoscale eddies, ubiquitous in the ETSP region, have been suggested to enhance vertical nutrient transport and thereby regulate primary productivity and hence organic matter export. Here, we investigated the impact of mesoscale eddies on anammox and denitrification activity using 15N-labelled in situ incubation experiments. Anammox was shown to be the dominant nitrogen loss process, but varied across the eddy, whereas denitrification was below detection at all stations. Anammox rates at the eddy periphery were greater than at the center. Similarly, depth-integrated chlorophyll paralleled anammox activity, increasing at the periphery relative to the eddy center; suggestive of enhanced organic matter export along the periphery supporting nitrogen loss. This can be attributed to enhanced vertical nutrient transport caused by an eddy-driven submesoscale mechanism operating at the eddy periphery. In the ETSP region, the widespread distribution of eddies and the large heterogeneity observed in anammox rates from a compilation of stations suggests that eddy-driven vertical nutrient transport may regulate offshore primary production and thereby nitrogen loss.

Mechanisms of P* Reduction in the Eastern Tropical South Pacific

Water masses influenced by oxygen minimum zones (OMZ) feature low inorganic nitrogen (N) to phosphorus (P) ratios. The surplus of P over N is thought to favor non-Redfield primary production by bloom-forming phytoplankton species. Additionally, excess phosphate (P*) is thought to provide a niche for nitrogen fixing organisms. In order to assess the effect of low inorganic nutrient ratios on the stoichiometry and composition of primary producers, biogeochemical measurements were carried out in 2012 during a research cruise in the eastern tropical South Pacific (ETSP). Based on pigment analyses, a succession of different phytoplankton functional groups was observed along onshore – offshore transects with diatoms dominating the productive upwelling region, and prymnesiophytes, cryptophytes and Synechococcus prevailing in the oligotrophic open ocean. Although inorganic nutrient supply ratios were below Redfield proportions throughout the sampling area, the stoichiometry of particulate organic nitrogen to phosphorus (PON:POP) generally exceeded ratios of 16:1. Despite PON:POP ≥ 16, high P* values in the surface layer (0-50 m) above the shelf rapidly decreased as water masses were advected offshore. There are three mechanisms which can explain these observations: (1) non-Redfield primary production, where the excess phosphorus in the biomass is directly released as dissolved organic phosphorus (DOP), (2) non-Redfield primary production, which is masked by a particulate organic matter pool mainly consisting of P-depleted detrital biomass, and/or (3) Redfield primary production combined with dinitrogen (N2) fixation. Our observations suggest that the three processes occur simultaneously in the study area; quantifying the relative importance of each of these mechanisms needs further investigation. Therefore, it remains uncertain whether the ETSP is a net sink for bioavailable N or whether the N-deficit in this area is replenished locally.

Objective estimates of mantle 3He in the ocean and implications for constraining the deep ocean circulation

Hydrothermal vents along the ocean's tectonic ridge systems inject superheated water and large amounts of dissolved metals that impact the deep ocean circulation and the oceanic cycling of trace metals. The hydrothermal fluid contains dissolved mantle helium that is enriched in 3He relative to the atmosphere, providing an isotopic tracer of the ocean's deep circulation and a marker of hydrothermal sources. This work investigates the potential for the 3He/4He isotope ratio to constrain the ocean's mantle 3He source and to provide constraints on the ocean's deep circulation. We use an ensemble of 11 data-assimilated steady-state ocean circulation models and a mantle helium source based on geographically varying sea-floor spreading rates. The global source distribution is partitioned into 6 regions, and the vertical profile and source amplitude of each region are varied independently to determine the optimal 3He source distribution that minimizes the mismatch between modeled and observed δ3He. In this way, we are able to fit the observed δ3He distribution to within a relative error of ∼15%, with a global 3He source that ranges from 640 to 850 mol yr−1, depending on circulation. The fit captures the vertical and interbasin gradients of the δ3He distribution very well and reproduces its jet-sheared saddle point in the deep equatorial Pacific. This demonstrates that the data-assimilated models have much greater fidelity to the deep ocean circulation than other coarse-resolution ocean models. Nonetheless, the modelled δ3He distributions still display some systematic biases, especially in the deep North Pacific where δ3He is overpredicted by our models, and in the southeastern tropical Pacific, where observed westward-spreading δ3He plumes are not well captured. Sources inferred by the data-assimilated transport with and without isopycnally aligned eddy diffusivity differ widely in the Southern Ocean, in spite of the ability to match the observed distributions of CFCs and radiocarbon for either eddy parameterization.

Chromophoric and fluorescent dissolved organic matter in and above the oxygen minimum zone off Peru

Key Points: - Two amino acid-like and three humic-like FDOM components were found in and above the oxygen minimum zone off the coast of Peru - The distribution of CDOM and amino acid-like FDOM covaried with chl a, suggesting phytoplankton as their major source - Presence of DOM microbial reworking and DOM release by anoxic sediment was illustrated by the distribution of humic-like FDOM As a result of nutrient upwelling, the Peruvian coastal system is one of the most productive regions in the ocean. Sluggish ventilation of intermediate waters, characteristic for the Eastern Tropical South Pacific (ETSP) and microbial degradation of a high organic matter load promotes deoxygenation at depth. Dissolved organic matter (DOM) plays a key role in microbial respiration and carbon cycling, but little is known on DOM distribution and cycling in the ETSP. DOM optical properties give important insights on DOM sources, structure and biogeochemical reactivity. Here, we present data and a conceptual view on distribution and cycling of chromophoric (CDOM) and fluorescent (FDOM) DOM in and above the oxygen minimum zone (OMZ) off Peru. Five fluorescent components were identified during PARAFAC analysis. Highest intensities of CDOM and of the amino acid-like fluorescent component (C3) occurred above the OMZ and coincided with maximum chl a concentrations, suggesting phytoplankton productivity as major source. High intensities of a marine humic-like fluorescent component (C1), observed in subsurface waters, indicated in situ microbial reworking of DOM. FDOM release from inner shelf sediment was determined by seawater analysis and continuous glider sensor measurement and included a humic-like component (C2) with a signature typical for terrestrially derived humic acids. Upwelling supplied humic-like substances to the euphotic zone. Photo-reactions were likely involved in the production of a humic-like fluorescent component (C5). Our data show that variable biological and physical processes need to be considered for understanding DOM cycling in a highly dynamic coastal upwelling system like the ETSP off Peru.

Vertical modeling of the nitrogen cycle in the eastern tropical South Pacific oxygen deficient zone using high‐resolution concentration and isotope measurements

AbstractMarine oxygen deficient zones (ODZs) have long been identified as sites of fixed nitrogen (N) loss. However, the mechanisms and rates of N loss have been debated, and traditional methods for measuring these rates are labor‐intensive and may miss hot spots in spatially and temporally variable environments. Here we estimate rates of heterotrophic nitrate reduction, heterotrophic nitrite reduction (denitrification), nitrite oxidation, and anaerobic ammonium oxidation (anammox) at a coastal site in the eastern tropical South Pacific (ETSP) ODZ based on high‐resolution concentration and natural abundance stable isotope measurements of nitrate (NO3−) and nitrite (NO2−). These measurements were used to estimate process rates using a two‐step inverse modeling approach. The modeled rates were sensitive to assumed isotope effects for NO3− reduction and NO2− oxidation. Nevertheless, we addressed two questions surrounding the fates of NO2− in the ODZ: (1) Is NO2− being primarily reduced to N2 or oxidized to NO3− in the ODZ? and (2) what are the contributions of anammox and denitrification to NO2− removal? Depth‐integrated rates from the model suggest that 72–88% of the NO2− produced in the ODZ was oxidized back to NO3−, while 12–28% of NO2− was reduced to N2. Furthermore, our model suggested that 36–74% of NO2− loss was due to anammox, with the remainder due to denitrification. These model results generally agreed with previously measured rates, though with a large range of uncertainty, and they provide a long‐term integrated view that compliments incubation experiments to obtain a broader picture of N cycling in ODZs.

A dissolved cobalt plume in the oxygen minimum zone of the eastern tropical South Pacific

Abstract. Cobalt is a nutrient to phytoplankton, but knowledge about its biogeochemical cycling is limited, especially in the Pacific Ocean. Here, we report sections of dissolved cobalt and labile dissolved cobalt from the US GEOTRACES GP16 transect in the South Pacific. The cobalt distribution is closely tied to the extent and intensity of the oxygen minimum zone in the eastern South Pacific with highest concentrations measured at the oxycline near the Peru margin. Below 200 m, remineralization and circulation produce an inverse relationship between cobalt and dissolved oxygen that extends throughout the basin. Within the oxygen minimum zone, elevated concentrations of labile cobalt are generated by input from coastal sources and reduced scavenging at low O2. As these high cobalt waters are upwelled and advected offshore, phytoplankton export returns cobalt to low-oxygen water masses underneath. West of the Peru upwelling region, dissolved cobalt is less than 10 pM in the euphotic zone and strongly bound by organic ligands. Because the cobalt nutricline within the South Pacific gyre is deeper than in oligotrophic regions in the North and South Atlantic, cobalt involved in sustaining phytoplankton productivity in the gyre is heavily recycled and ultimately arrives from lateral transport of upwelled waters from the eastern margin. In contrast to large coastal inputs, atmospheric deposition and hydrothermal vents along the East Pacific Rise appear to be minor sources of cobalt. Overall, these results demonstrate that oxygen biogeochemistry exerts a strong influence on cobalt cycling.

Elevated trace metal content of prokaryotic communities associated with marine oxygen deficient zones

AbstractLittle is known about the trace metal content of marine prokaryotes, in part due to their co‐occurrence with more abundant particulate phases in the upper ocean, such as phytoplankton and biogenic detritus, lithogenic minerals, and authigenic Mn and Fe oxyhydroxides. We attempt to isolate these biomass signals in particulate data from the US GEOTRACES Eastern Pacific Zonal Transect (cruise GP16) in the Eastern Tropical South Pacific (ETSP), which exhibited consistent maxima in P and other bioactive trace metals, and minima in particulate Mn, in the oxygen deficient zones (ODZs) of 13 stations. Nitrite maxima and nitrate deficits indicated the presence of denitrifying prokaryotic biomass within ETSP ODZs, and deep secondary fluorescence maxima at the upper ODZ boundaries of 10 stations also suggested the presence of low‐light, autotrophic communities. ODZs were observed as far west as 99°W, more than 2300 km from the South American coast, where eolian lithogenic and lateral/resuspended sedimentary inputs were negligible, presenting a unique opportunity to examine prokaryotic metal stoichiometries. ODZ particulate P maxima can rival gyre mixed layer biomass concentrations, are highly sensitive to oxygen, and are in excess of amounts scavengable by local Fe oxyhydroxides and acid–volatile sulfides. Even after correction for lithogenic and ferruginous–scavenged metals, ODZ P‐maxima are often enriched in Cd, Co, Cu, Ni, V, and Zn, exhibiting particulate trace metal ratios to P that exceed mixed layer biomass ratios by factors of 2–9. ODZ prokaryotic communities may be largely hidden, TM–rich pools involved in the marine cycles of these bioactive trace metals.

Box-modelling of the impacts of atmospheric nitrogen deposition and benthic remineralisation on the nitrogen cycle of the eastern tropical South Pacific

Abstract. Both atmospheric deposition and benthic remineralisation influence the marine nitrogen cycle, and hence ultimately also marine primary production. The biological and biogeochemical relations in the eastern tropical South Pacific (ETSP) among nitrogen deposition, benthic denitrification and phosphorus regeneration are analysed in a prognostic box model of the oxygen, nitrogen and phosphorus cycles in the ETSP. Atmospheric nitrogen deposition ( ≈ 1.5 Tg N yr−1 for the years 2000–2009) is offset by half in the model by reduced N2 fixation, with the other half transported out of the model domain. Model- and data-based benthic denitrification in our model domain are responsible for losses of 0.19 and 1.0 Tg Tg N yr−1, respectively, and both trigger nitrogen fixation, partly compensating for the NO3− loss. Model- and data-based estimates of enhanced phosphate release via sedimentary phosphorus regeneration under suboxic conditions are 0.062 and 0.11 Tg N yr−1, respectively. Since phosphate is the ultimate limiting nutrient in the model, even very small additional phosphate inputs stimulate primary production and subsequent export production and NO3− loss in the oxygen minimum zone (OMZ). A sensitivity analysis of the local response to both atmospheric deposition and benthic remineralisation indicates dominant stabilising feedbacks in the ETSP, which tend to keep a balanced nitrogen inventory; i.e. nitrogen input by atmospheric deposition is counteracted by decreasing nitrogen fixation; NO3− loss via benthic denitrification is partly compensated for by increased nitrogen fixation; enhanced nitrogen fixation stimulated by phosphate regeneration is partly counteracted by stronger water-column denitrification. Even though the water column in our model domain acts as a NO3− source, the ETSP including benthic denitrification might be a NO3− sink.

Ammonium excretion and oxygen respiration of tropical copepods and euphausiids exposed to oxygen minimum zone conditions

Abstract. Calanoid copepods and euphausiids are key components of marine zooplankton communities worldwide. Most euphausiids and several copepod species perform diel vertical migrations (DVMs) that contribute to the export of particulate and dissolved matter to midwater depths. In vast areas of the global ocean, and in particular in the eastern tropical Atlantic and Pacific, the daytime distribution depth of many migrating organisms corresponds to the core of the oxygen minimum zone (OMZ). At depth, the animals experience reduced temperature and oxygen partial pressure (pO2) and an increased carbon dioxide partial pressure (pCO2) compared to their near-surface nighttime habitat. Although it is well known that low oxygen levels can inhibit respiratory activity, the respiration response of tropical copepods and euphausiids to relevant pCO2, pO2, and temperature conditions remains poorly parameterized. Further, the regulation of ammonium excretion at OMZ conditions is generally not well understood. It was recently estimated that DVM-mediated ammonium supply could fuel bacterial anaerobic ammonium oxidation – a major loss process for fixed nitrogen in the ocean considerably. These estimates were based on the implicit assumption that hypoxia or anoxia in combination with hypercapnia (elevated pCO2) does not result in a down-regulation of ammonium excretion. We exposed calanoid copepods from the Eastern Tropical North Atlantic (ETNA; Undinula vulgaris and Pleuromamma abdominalis) and euphausiids from the Eastern Tropical South Pacific (ETSP; Euphausia mucronata) and the ETNA (Euphausia gibboides) to different temperatures, carbon dioxide and oxygen levels to study their survival, respiration and excretion rates at these conditions. An increase in temperature by 10 °C led to an approximately 2-fold increase of the respiration and excretion rates of U. vulgaris (Q10, respiration = 1.4; Q10, NH4-excretion = 1.6), P. abdominalis (Q10, respiration = 2.0; Q10, NH4-excretion = 2.4) and E. gibboides (Q10, respiration = 2.0; Q10, NH4-excretion = 2.4; E. mucronata not tested). Exposure to differing carbon dioxide levels had no overall significant impact on the respiration or excretion rates. Species from the ETNA were less tolerant to low oxygen levels than E. mucronata from the ETSP, which survived exposure to anoxia at 13 °C. Respiration and excretion rates were reduced upon exposure to low oxygen levels, albeit at different species-specific levels. Reduction of the excretion and respiration rates in ETNA species occurred at a pO2 of 0.6 (P. abdominalis) and 2.4 kPa (U. vulgaris and E. gibboides) at OMZ temperatures. Such low oxygen levels are normally not encountered by these species in the ETNA. E. mucronata however regularly migrates into the strongly hypoxic to anoxic core of the ETSP OMZ. Exposure to low oxygen levels led to a strong reduction of respiration and ammonium excretion in E. mucronata (pcrit respiration = 0.6, pcrit NH4-excretion = 0.73). A drastic reduction of respiratory activity was also observed by other authors for euphausiids, squat lobsters and calanoid copepods, but was not yet accounted for when calculating DVM-mediated active fluxes into the ETSP OMZ. Current estimates of DVM-mediated active export of carbon and nitrogen into the ETSP OMZ are therefore likely too high and future efforts to calculate these export rates should take the physiological responses of migratory species to OMZ conditions into account.

Low rates of nitrogen fixation in eastern tropical South Pacific surface waters

An extensive region of the Eastern Tropical South Pacific (ETSP) Ocean has surface waters that are nitrate-poor yet phosphate-rich. It has been proposed that this distribution of surface nutrients provides a geochemical niche favorable for N2fixation, the primary source of nitrogen to the ocean. Here, we present results from two cruises to the ETSP where rates of N2fixation and its contribution to export production were determined with a suite of geochemical and biological measurements. N2fixation was only detectable using nitrogen isotopic mass balances at two of six stations, and rates ranged from 0 to 23 µmol N m(-2)d(-1)based on sediment trap fluxes. Whereas the fractional importance of N2fixation did not change, the N2-fixation rates at these two stations were several-fold higher when scaled to other productivity metrics. Regardless of the choice of productivity metric these N2-fixation rates are low compared with other oligotrophic locations, and the nitrogen isotope budgets indicate that N2fixation supports no more than 20% of export production regionally. Although euphotic zone-integrated short-term N2-fixation rates were higher, up to 100 µmol N m(-2)d(-1), and detected N2fixation at all six stations, studies of nitrogenase gene abundance and expression from the same cruises align with the geochemical data and together indicate that N2fixation is a minor source of new nitrogen to surface waters of the ETSP. This finding is consistent with the hypothesis that, despite a relative abundance of phosphate, iron may limit N2fixation in the ETSP.