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For millennia, humans have gravitated towards coastlines for their resource potential and as geopolitical centres for global trade. A basic requirement ensuring water security for coastal communities relies on a delicate balance between the supply and demand of potable water. The interaction between freshwater and saltwater in coastal settings is, therefore, complicated by both natural and human-driven environmental changes at the land–sea interface. In particular, ongoing sea-level rise, warming and deoxygenation might exacerbate such perturbations. In this context, an improved understanding of the nature and variability of groundwater fluxes across the land–sea continuum is timely yet remains out of reach. The flow of terrestrial groundwater across the coastal transition zone and the extent of freshened groundwater below the present-day seafloor are receiving increased attention in marine and coastal sciences because they likely represent a significant yet highly uncertain component of (bio)geochemical budgets and because of the emerging interest in the potential use of offshore freshened groundwater as a resource. At the same time, “reverse” groundwater flux from offshore to onshore is of prevalent socio-economic interest, as terrestrial groundwater resources are continuously pressured by over-pumping and seawater intrusion in many coastal regions worldwide. An accurate assessment of the land–ocean connectivity through groundwater and its potential responses to future anthropogenic activities and climate change will require a multidisciplinary approach combining the expertise of geophysicists, hydrogeologists, (bio)geochemists and modellers. Such joint activities will lay the scientific basis for better understanding the role of groundwater in societally relevant issues such as climate change, pollution and the environmental status of the coastal oceans within the framework of the United Nations Sustainable Development Goals. Here, we present our perspectives on future research directions to better understand land–ocean connectivity through groundwater, including the spatial distributions of the essential hydrogeological parameters, highlighting technical and scientific developments and briefly discussing the societal relevance of that connectivity in rapidly changing coastal oceans.

Dissolved methane (CH4) was measured at 9 stations along a transect at 75° S in the Ross Sea during austral summer in January 2020. CH4 undersaturation (mean: 82 ± 20 %) was found in the water column, with a mean air-sea CH4 flux density of −0.58 ± 0.48 μmol m−2 day−1, which suggests that the Ross Sea was a net sink for atmospheric CH4 during the austral summer. Simple box-model calculations revealed that the CH4 depletion should occur in the surface mixed layer because of CH4 oxidation and advection of CH4-poor waters. We propose that freshwater injection caused by sea-ice melting in summer dilutes CH4 concentrations within the surface layer and thus increases its potential for atmospheric CH4 uptake in the Ross Sea. Thus, we argue that both CH4 consumption and sea-ice melting are important drivers of CH4 undersaturation, which implies that the high-latitude area of the Southern Ocean is a sink for atmospheric CH4. We estimated that the Southern Ocean (> 65° S) takes up about 0.02 % of the global CH4 emissions and thus represents a minor sink for atmospheric CH4.

Data availability. The microarray data presented here are available via GEO (Gene Expression Omnibus; http://www.ncbi.nlm.nih.gov/ geo/, NCBI, 2020) at NCBI (National Center for Biotechnology Information) under GEO accession no GSE142806. The N2O production rates were archived in the PANGAEA data archive (https: //doi.pangaea.de/10.1594/PANGAEA.914948, Frey et al., 2020). The N2O data are available from the Marine Methane and Nitrous Oxide (MEMENTO) database (https://memento.geomar.de/de/n2o, last access: 16 April 2020; Kock and Bange, 2015)., Supplement. The supplement related to this article is available online at: https://doi.org/10.5194/bg-17-2263-2020-supplement., 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., German Research Foundation (DFG) SFB754, Deutscher Akademischer Austausch Dienst (DAAD) 57350888, China Scholarship Council 201406330054, Universidad de Granada, European Union (EU) 704272, Villum Foundation 16518, National Science Foundation (NSF) OCE-1657663, Spanish Government 014/02917

Depth profiles of nitrous oxide (N2O) were measured during six cruises to the upwelling area and oxygen minimum zone (OMZ) off Peru in 2009 and 2012/2013, covering both the coastal shelf region and the adjacent open ocean. N2O profiles displayed a strong sensitivity towards oxygen concentrations. Open ocean profiles with distances to the shelf break larger than the first baroclinic Rossby radius of deformation showed a transition from a broad maximum close to the Equator to a double-peak structure south of 5° S where the oxygen minimum was more pronounced. Maximum N2O concentrations in the open ocean were about 80 nM. A linear relationship between ΔN2O and apparent oxygen utilization (AOU) could be found for measurements within the upper oxycline, with a slope similar to studies in other oceanic regions. In contrast, N2O profiles close to the shelf revealed a much higher variability, and N2O concentrations higher than 100 nM were often observed. The highest N2O concentration measured at the shelf was ∼ 850 nM. Due to the extremely sharp oxygen gradients at the shelf, N2O maxima occurred in very shallow water depths of less than 50 m. In the coastal area, a linear relationship between ΔN2O and AOU could not be observed as extremely high ΔN2O values were scattered over the full range of oxygen concentrations. The data points that showed the strongest deviation from a linear ΔN2O ∕ AOU relationship also showed signals of intense nitrogen loss. These results indicate that the coastal upwelling at the Peruvian coast and the subsequent strong remineralization in the water column causes conditions that lead to extreme N2O accumulation, most likely due to the interplay of intense mixing and high rates of remineralization which lead to a rapid switching of the OMZ waters between anoxic and oxic conditions. This, in turn, could trigger incomplete denitrification or pulses of increased nitrification with extreme N2O production.

While being a major source for atmospheric CO2 the Peruvian upwelling region exhibits strong variability in surface fCO2 on short spatial and temporal scales. Understanding the physical processes driving the strong variability is of fundamental importance for constraining the effect of marine emissions from upwelling regions on the global CO2 budget. In this study, a frontal decay on length scales of 𝒪(10 km) was observed off the Peruvian coast following a pronounced decrease in downfrontal wind speed with a time lag of 9 hours. Simultaneously, the sea-to-air flux of CO2 on the inshore (cold) side of the front dropped from up to 80 to 10 mmol m-2 day-1, while the offshore (warm) side of the front was constantly outgassing at a rate of 10–20 mmol m-2 day-1. Based on repeated ship transects the decay of the front was observed to occur in two phases. The first phase was characterized by a development of coherent surface temperature anomalies which gained in amplitude over 6–9 hours. The second phase was characterized by a disappearance of the surface temperature front within 6 hours. Submesoscale mixed layer instabilities were present but seem too slow to completely remove the temperature gradient in this short time period. Dynamics such as a pressure driven gravity current appear to be a likely mechanism behind the evolution of the front.

A new system for continuous, highly resolved oceanic and atmospheric measurements of N2O, CO and CO2 is described. The system is based upon off-axis integrated cavity output spectroscopy (OA-ICOS) and a non-dispersive infrared analyzer (NDIR), both coupled to a Weiss-type equilibrator. Performance of the combined setup was evaluated by testing its precision, accuracy, long-term stability, linearity and response time. Furthermore, the setup was tested during two oceanographic campaigns in the equatorial Atlantic Ocean in order to explore its potential for autonomous deployment onboard voluntary observing ships (VOS). Improved equilibrator response times for N2O (2.5 min) and CO (45 min) were achieved in comparison to response times from similar chamber designs used by previous studies. High stability of the OA-ICOS analyzer was demonstrated by low optimal integration times of 2 and 4 min for N2O and CO respectively, as well as detection limits of < 40 ppt and precision better than 0.3 ppb Hz–1/2. Results from a direct comparison of the method presented here and well-established discrete methods for oceanic N2O and CO2 measurements showed very good consistency. The favorable agreement between underway atmospheric N2O, CO and CO2 measurements and monthly means at Ascension Island (7.96° S 14.4° W) further suggests a reliable operation of the underway setup in the field. The potential of the system as an improved platform for measurements of trace gases was explored by using continuous N2O and CO2 data to characterize the development of the seasonal equatorial upwelling in the Atlantic Ocean during two R/V Maria S. Merian cruises. A similar record of high-resolution CO measurements was simultaneously obtained, offering, for the first time, the possibility of a comprehensive view of the distribution and emissions of these climate-relevant gases in the area studied. The relatively simple underway N2O/CO/CO2 setup is suitable for long-term deployment onboard research and commercial vessels although potential sources of drift, such as cavity temperature, and further technical improvements towards automation, still need to be addressed.

The climate active trace-gas carbonyl sulfide (OCS) is the most abundant sulfur gas in the atmosphere. A missing source in its atmospheric budget is currently suggested, resulting from an upward revision of the vegetation sink in top-down approaches. Oceanic emissions have been proposed to close the resulting gap in the atmospheric budget. We present a bottom-up approach including new observations of OCS in surface waters of the tropical Atlantic, Pacific and Indian oceans to show that direct OCS emissions are insufficient to account for the missing source. Extrapolation of our observations using a biogeochemical box model suggests oceanic net uptake instead of emission for the entire tropical ocean area and, further, a global ocean source strength well below that suggested by top-down estimates. This bottom-up estimate of oceanic emissions has implications for using OCS as a proxy for terrestrial CO2 uptake, which is currently hampered by the inadequate quantification of atmospheric OCS sources and sinks.

Depth profiles of nitrous oxide (N2O) were measured during six cruises to the upwelling area and oxygen minimum zone (OMZ) off Peru in 2009 and 2012/13, covering both the coastal shelf region and the adjacent open ocean. N2O profiles displayed a strong sensitivity towards oxygen concentrations. Open ocean profiles showed a transition from a broad maximum to a double-peak structure towards the centre of the OMZ where the oxygen minimum was more pronounced. Maximum N2O concentrations in the open ocean were about 80 nM. A linear relationship between ΔN2O and apparent oxygen utilization (AOU) could be found for all measurements within the upper oxycline, with a slope similar to studies in other oceanic regions. N2O profiles close to the shelf revealed a much higher variability, with N2O concentrations in the upper oxycline reaching up to several hundred nanomoles per liter at selected stations. Due to the extremely sharp oxygen gradients at the shelf, these maxima occurred in very shallow water depths of less than 50 m. In this area, a linear relationship between ΔN2O and AOU could not be observed. N2O concentrations above 100 nM were observed at oxygen concentrations ranging from close to saturation to suboxic conditions. Our results indicate that the coastal upwelling off Peru at the shelf causes conditions that lead to extreme N2O accumulation.