Description: The intraseasonal evolution of physical and biogeochemical properties during a coastal trapped wave event off central Peru is analysed using data from an extensive shipboard observational programme conducted between April and June 2017, and remote sensing data. The poleward velocities in the Peru–Chile Undercurrent were highly variable and strongly intensified to above 0.5 m s−1 between the middle and end of May. This intensification was likely caused by a first-baroclinic-mode downwelling coastal trapped wave, excited by a westerly wind anomaly at the Equator and originating at about 95∘ W. Local winds along the South American coast did not impact the wave. Although there is general agreement between the observed cross-shore-depth velocity structure of the coastal trapped wave and the velocity structure of first vertical mode solution of a linear wave model, there are differences in the details of the two flow distributions. The enhanced poleward flow increased water mass advection from the equatorial current system to the study site. The resulting shorter alongshore transit times between the Equator and the coast off central Peru led to a strong increase in nitrate concentrations, less anoxic water, likely less fixed nitrogen loss to N2 and a decrease of the nitrogen deficit compared to the situation before the poleward flow intensification. This study highlights the role of changes in the alongshore advection due to coastal trapped waves for the nutrient budget and the cumulative strength of N cycling in the Peruvian oxygen minimum zone. Enhanced availability of nitrate may impact a range of pelagic and benthic elemental cycles, as it represents a major electron acceptor for organic carbon degradation during denitrification and is involved in sulfide oxidation in sediments.

Description: The speciation of dissolved iron (DFe) in the ocean is widely assumed to consist almost exclusively of Fe(III)-ligand complexes. Yet in most aqueous environments a poorly defined fraction of DFe also exists as Fe(II), the speciation of which is uncertain. Here we deploy flow injection analysis to measure in situ Fe(II) concentrations during a series of mesocosm/microcosm/multistressor experiments in coastal environments in addition to the decay rate of this Fe(II) when moved into the dark. During five mesocosm/microcosm/multistressor experiments in Svalbard and Patagonia, where dissolved (0.2 µm) Fe and Fe(II) were quantified simultaneously, Fe(II) constituted 24 %–65 % of DFe, suggesting that Fe(II) was a large fraction of the DFe pool. When this Fe(II) was allowed to decay in the dark, the vast majority of measured oxidation rate constants were less than calculated constants derived from ambient temperature, salinity, pH, and dissolved O2. The oxidation rates of Fe(II) spikes added to Atlantic seawater more closely matched calculated rate constants. The difference between observed and theoretical decay rates in Svalbard and Patagonia was most pronounced at Fe(II) concentrations 〈2 nM, suggesting that the effect may have arisen from organic Fe(II) ligands. This apparent enhancement of Fe(II) stability under post-bloom conditions and the existence of such a high fraction of DFe as Fe(II) challenge the assumption that DFe speciation in coastal seawater is dominated by ligand bound-Fe(III) species.

Description: Sediments in oxygen-depleted marine environments can be an important sink or source of bio-essential trace metals in the ocean. However, the key mechanisms controlling the release from or burial of trace metals in sediments are not exactly understood. Here, we investigate the benthic biogeochemical cycling of Fe and Cd in the oxygen minimum zone off Peru. We combine bottom water profiles, pore water profiles, as well as benthic fluxes determined from pore water profiles and in-situ from benthic chamber incubations along a depth transect at 12° S. In agreement with previous studies, both concentration-depth profiles and in-situ benthic fluxes indicate a Fe release from sediments into bottom waters. Diffusive Fe fluxes and Fe fluxes from benthic chamber incubations are roughly consistent (0.3–17.1 mmol m−2 y−1), indicating that diffusion is the main transport mechanism of dissolved Fe across the sediment-water interface. The occurrence of mats of sulfur oxidizing bacteria on the seafloor represents an important control on the spatial distribution of Fe fluxes by regulating hydrogen sulfide (H2S) concentrations and, potentially, Fe sulfide precipitation within the surface sediment. Removal of dissolved Fe after its release to anoxic bottom waters is rapid in the first 4 m away from the seafloor (half-life 〈 3 min) which hints to oxidative removal by nitrite or interaction with particles in the benthic boundary layer. Benthic flux estimates of Cd are indicative of a flux into the sediment within the oxygen minimum zone. Fluxes from benthic chamber incubations (up to 22.6 µmol m−2 y−1) exceed the diffusive fluxes (〈 1 µmol m−2 y−1) by a factor 〉 25, indicating that downward diffusion of Cd across the sediment-water interface is of subordinate importance for Cd removal from benthic chambers. As Cd removal in benthic chambers co-varies with H2S concentrations in the pore water of surface sediments, we argue that Cd removal is mediated by precipitation of CdS within the chamber. A mass balance approach, taking into account the contributions of diffusive fluxes and fluxes measured in benthic chambers as well as Cd delivery with organic material suggests that CdS precipitation in the near-bottom water could make an important contribution to the overall Cd mass accumulation in the sediment solid phase. According to our results, the solubility of trace metal sulfide minerals (Cd 〈〈 Fe) is a key-factor controlling trace metal removal and consequently the magnitude as well as the temporal and spatial heterogeneity of sedimentary fluxes. We argue that depending on their sulfide solubility, sedimentary source or sink fluxes of trace metals will change differentially as a result of declining oxygen concentrations and an associated expansion of sulfidic surface sediments. Such a trend could cause a change in the trace metal stoichiometry of upwelling water masses with potential consequences for marine ecosystems in the surface ocean.

Description: Freshwater discharge from glaciers is increasing across the Arctic in response to anthropogenic climate change, which raises questions about the potential downstream effects in the marine environment. Whilst a combination of long-term monitoring programmes and intensive Arctic field campaigns have improved our knowledge of glacier–ocean interactions in recent years, especially with respect to fjord/ocean circulation, there are extensive knowledge gaps concerning how glaciers affect marine biogeochemistry and productivity. Following two cross-cutting disciplinary International Arctic Science Committee (IASC) workshops addressing the importance of glaciers for the marine ecosystem, here we review the state of the art concerning how freshwater discharge affects the marine environment with a specific focus on marine biogeochemistry and biological productivity. Using a series of Arctic case studies (Nuup Kangerlua/Godthåbsfjord, Kongsfjorden, Kangerluarsuup Sermia/Bowdoin Fjord, Young Sound and Sermilik Fjord), the interconnected effects of freshwater discharge on fjord–shelf exchange, nutrient availability, the carbonate system, the carbon cycle and the microbial food web are investigated. Key findings are that whether the effect of glacier discharge on marine primary production is positive or negative is highly dependent on a combination of factors. These include glacier type (marine- or land-terminating), fjord–glacier geometry and the limiting resource(s) for phytoplankton growth in a specific spatio-temporal region (light, macronutrients or micronutrients). Arctic glacier fjords therefore often exhibit distinct discharge–productivity relationships, and multiple case-studies must be considered in order to understand the net effects of glacier discharge on Arctic marine ecosystems.

Description: Oxygen-deficient zones (ODZs) are major sites of net natural nitrous oxide (N2O) production and emissions. In order to understand changes in the magnitude of N2O production in response to global change, knowledge on the individual contributions of the major microbial pathways (nitrification and denitrification) to N2O production and their regulation is needed. In the ODZ in the coastal area off Peru, the sensitivity of N2O production to oxygen and organic matter was investigated using 15N tracer experiments in combination with quantitative PCR (qPCR) and microarray analysis of total and active functional genes targeting archaeal amoA and nirS as marker genes for nitrification and denitrification, respectively. Denitrification was responsible for the highest N2O production with a mean of 8.7 nmol L−1 d−1 but up to 118±27.8 nmol L−1 d−1 just below the oxic–anoxic interface. The highest N2O production from ammonium oxidation (AO) of 0.16±0.003 nmol L−1 d−1 occurred in the upper oxycline at O2 concentrations of 10–30 µmol L−1 which coincided with the highest archaeal amoA transcripts/genes. Hybrid N2O formation (i.e., N2O with one N atom from NH+4 and the other from other substrates such as NO−2) was the dominant species, comprising 70 %–85 % of total produced N2O from NH+4, regardless of the ammonium oxidation rate or O2 concentrations. Oxygen responses of N2O production varied with substrate, but production and yields were generally highest below 10 µmol L−1 O2. Particulate organic matter additions increased N2O production by denitrification up to 5-fold, suggesting increased N2O production during times of high particulate organic matter export. High N2O yields of 2.1 % from AO were measured, but the overall contribution by AO to N2O production was still an order of magnitude lower than that of denitrification. Hence, these findings show that denitrification is the most important N2O production process in low-oxygen conditions fueled by organic carbon supply, which implies a positive feedback of the total oceanic N2O sources in response to increasing oceanic deoxygenation.

Description: The eastern boundary region of the southeastern Pacific Ocean hosts one of the world's most dynamic and productive upwelling systems with an associated oxygen minimum zone (OMZ). The variability in downward export fluxes in this region, with strongly varying surface productivity, upwelling intensities and water column oxygen content, is however poorly understood. Thorium-234 (234Th) is a powerful tracer to study the dynamics of export fluxes of carbon and other elements, yet intense advection and diffusion in nearshore environments impact the assessment of depth-integrated 234Th fluxes when not properly evaluated. Here we use vessel-mounted acoustic Doppler current profiler (VmADCP) current velocities, satellite wind speed and in situ microstructure measurements to determine the magnitude of advective and diffusive fluxes over the entire 234Th flux budget at 25 stations from 11 to 16∘ S in the Peruvian OMZ. Contrary to findings along the GEOTRACES P16 eastern section, our results showed that weak surface wind speed during our cruises induced low upwelling rates and minimal upwelled 234Th fluxes, whereas vertical diffusive 234Th fluxes were important only at a few shallow shelf stations. Horizontal advective and diffusive 234Th fluxes were negligible because of small alongshore 234Th gradients. Our data indicated a poor correlation between seawater 238U activity and salinity. Assuming a linear relationship between the two would lead to significant underestimations of the total 234Th flux by up to 40 % in our study. Proper evaluation of both physical transport and variability in 238U activity is thus crucial in coastal 234Th flux studies. Finally, we showed large temporal variations on 234Th residence times across the Peruvian upwelling zone and cautioned future carbon export studies to take these temporal variabilities into consideration while evaluating carbon export efficiency.

Description: The extracellular concentration of H2O2 in surface aquatic environments is controlled by a balance between photochemical production and the microbial synthesis of catalase and peroxidase enzymes to remove H2O2 from solution. In any kind of incubation experiment, the formation rates and equilibrium concentrations of reactive oxygen species (ROSs) such as H2O2 may be sensitive to both the experiment design, particularly to the regulation of incident light, and the abundance of different microbial groups, as both cellular H2O2 production and catalase–peroxidase enzyme production rates differ between species. Whilst there are extensive measurements of photochemical H2O2 formation rates and the distribution of H2O2 in the marine environment, it is poorly constrained how different microbial groups affect extracellular H2O2 concentrations, how comparable extracellular H2O2 concentrations within large-scale incubation experiments are to those observed in the surface-mixed layer, and to what extent a mismatch with environmentally relevant concentrations of ROS in incubations could influence biological processes differently to what would be observed in nature. Here we show that both experiment design and bacterial abundance consistently exert control on extracellular H2O2 concentrations across a range of incubation experiments in diverse marine environments. During four large-scale (〉1000 L) mesocosm experiments (in Gran Canaria, the Mediterranean, Patagonia and Svalbard) most experimental factors appeared to exert only minor, or no, direct effect on H2O2 concentrations. For example, in three of four experiments where pH was manipulated to 0.4–0.5 below ambient pH, no significant change was evident in extracellular H2O2 concentrations relative to controls. An influence was sometimes inferred from zooplankton density, but not consistently between different incubation experiments, and no change in H2O2 was evident in controlled experiments using different densities of the copepod Calanus finmarchicus grazing on the diatom Skeletonema costatum (〈1 % change in [H2O2] comparing copepod densities from 1 to 10 L−1). Instead, the changes in H2O2 concentration contrasting high- and low-zooplankton incubations appeared to arise from the resulting changes in bacterial activity. The correlation between bacterial abundance and extracellular H2O2 was stronger in some incubations than others (R2 range 0.09 to 0.55), yet high bacterial densities were consistently associated with low H2O2. Nonetheless, the main control on H2O2 concentrations during incubation experiments relative to those in ambient, unenclosed waters was the regulation of incident light. In an open (lidless) mesocosm experiment in Gran Canaria, H2O2 was persistently elevated (2–6-fold) above ambient concentrations; whereas using closed high-density polyethylene mesocosms in Crete, Svalbard and Patagonia H2O2 within incubations was always reduced (median 10 %–90 %) relative to ambient waters.

Description: Eastern boundary upwelling systems (EBUS) are among the most productive marine ecosystems on Earth. The production of organic material is fueled by upwelling of nutrient-rich deep waters and high incident light at the sea surface. However, biotic and abiotic factors can modify surface production and related biogeochemical processes. Determining these factors is important because EBUS are considered hotspots of climate change, and reliable predictions of their future functioning requires understanding of the mechanisms driving the biogeochemical cycles therein. In this field experiment, we used in situ mesocosms as tools to improve our mechanistic understanding of processes controlling organic matter cycling in the coastal Peruvian upwelling system. Eight mesocosms, each with a volume of ∼55 m3, were deployed for 50 d ∼6 km off Callao (12∘ S) during austral summer 2017, coinciding with a coastal El Niño phase. After mesocosm deployment, we collected subsurface waters at two different locations in the regional oxygen minimum zone (OMZ) and injected these into four mesocosms (mixing ratio ≈1.5 : 1 mesocosm: OMZ water). The focus of this paper is on temporal developments of organic matter production, export, and stoichiometry in the individual mesocosms. The mesocosm phytoplankton communities were initially dominated by diatoms but shifted towards a pronounced dominance of the mixotrophic dinoflagellate (Akashiwo sanguinea) when inorganic nitrogen was exhausted in surface layers. The community shift coincided with a short-term increase in production during the A. sanguinea bloom, which left a pronounced imprint on organic matter C : N : P stoichiometry. However, C, N, and P export fluxes did not increase because A. sanguinea persisted in the water column and did not sink out during the experiment. Accordingly, export fluxes during the study were decoupled from surface production and sustained by the remaining plankton community. Overall, biogeochemical pools and fluxes were surprisingly constant for most of the experiment. We explain this constancy by light limitation through self-shading by phytoplankton and by inorganic nitrogen limitation which constrained phytoplankton growth. Thus, gain and loss processes remained balanced and there were few opportunities for blooms, which represents an event where the system becomes unbalanced. Overall, our mesocosm study revealed some key links between ecological and biogeochemical processes for one of the most economically important regions in the oceans.

Description: The extensive use of silver nanoparticles (AgNPs) in consumer products, medicine, and industry leads to their release into the environment. Thus, a characterization of the concentration, size, fate, and toxicity of AgNPs under environmental conditions is required. In this study, we present the characterization and optimization of an asymmetric flow field-flow fractionation (AF4) system coupled with UV/Vis spectrophotometer and dynamic light scattering (DLS) detector as a powerful tool for the size separation and multi-parameter characterization of AgNPs in complex matrices. The hyphenated AF4-UV/Vis-DLS system was first characterized using individual injections of the different size fractions. We used electrostatically stabilized AgNPs of 20-, 50-, and 80-nm nominal diameters coated with lipoic acid. We investigated the effect of applied cross-flows, carrier solutions, focus times, and quantity of injected particles on the nature of the AF4 fractograms and on the integrity of the AgNPs. Best size separation of a 1:1 mixture of 20- and 80-nm AgNPs was achieved using cross-flows of 0.5 and 0.7 mL/min with 1 mM NaCl and 0.05% v/v Mucasol as carrier solutions. We also researched the behavior of AgNPs in natural waters using the hyphenated AF4-UV/Vis-DLS system, under determined optimal conditions.

Description: A new box model is employed to simulate the oxygen-dependent cycling of nutrients in the Peruvian oxygen minimum zone (OMZ). Model results and data for the present state of the OMZ indicate that dissolved iron is the limiting nutrient for primary production and is provided by the release of dissolved ferrous iron from shelf and slope sediments. Most of the removal of reactive nitrogen occurs by anaerobic oxidation of ammonium where ammonium is delivered by aerobic organic nitrogen degradation. Model experiments simulating the effects of ocean deoxygenation and warming show that the productivity of the Peruvian OMZ will increase due to the enhanced release of dissolved iron from shelf and slope sediments. A positive feedback loop rooted in the oxygen-dependent benthic iron release amplifies, both, the productivity rise and oxygen decline in ambient bottom waters. Hence, a 1% decline in oxygen supply reduces oxygen concentrations in sub-surface waters of the continental margin by 22%. The trend towards enhanced productivity and amplified deoxygenation will continue until further phytoplankton growth is limited by the loss of reactive nitrogen. Under nitrogen-limitation, the redox state of the OMZ is stabilized by negative feedbacks. A further increase in productivity and transition to sulfidic conditions is only possible if the rate of nitrogen fixation increases drastically under anoxic conditions. Such a transition would lead to a wide-spread accumulation of toxic sulfide with detrimental consequences for fishery yields in the Peruvian OMZ that currently provides a significant fraction of the global fish catch.