In the oligotrophic waters of the Mediterranean Sea, during the stratification period, the microbial loop relies on pulsed inputs of nutrients through the atmospheric deposition of aerosols from both natural (e.g., Saharan dust), anthropogenic, or mixed origins. While the influence of dust deposition on microbial processes and community composition is still not fully constrained, the extent to which future environmental conditions will affect dust inputs and the microbial response is not known. The impact of atmospheric wet dust deposition was studied both under present and future environmental conditions (+3 ∘C warming and acidification of −0.3 pH units), through experiments in 300 L climate reactors. In total, three Saharan dust addition experiments were performed with surface seawater collected from the Tyrrhenian Sea, Ionian Sea, and Algerian basin in the western Mediterranean Sea during the PEACETIME (ProcEss studies at the Air–sEa Interface after dust deposition in the MEditerranean sea) cruise in May–June 2017. Top-down controls on bacteria, viral processes, and community, as well as microbial community structure (16S and 18S rDNA amplicon sequencing), were followed over the 3–4 d experiments. Different microbial and viral responses to dust were observed rapidly after addition and were, most of the time, more pronounced when combined with future environmental conditions. The dust input of nutrients and trace metals changed the microbial ecosystem from a bottom-up limited to a top-down controlled bacterial community, likely from grazing and induced lysogeny. The relative abundance of mixotrophic microeukaryotes and phototrophic prokaryotes also increased. Overall, these results suggest that the effect of dust deposition on the microbial loop is dependent on the initial microbial assemblage and metabolic state of the tested water and that predicted warming and acidification will intensify these responses, affecting food web processes and biogeochemical cycles.
This study reports the only recent characterization of two contrasted wet deposition events collected during the PEACETIME (ProcEss studies at the Air–sEa Interface after dust deposition in the MEditerranean Sea) cruise in the open Mediterranean Sea (Med Sea) and their impact on trace metal (TM) marine stocks. Rain samples were analysed for Al, 12 TMs (Co, Cd, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Ti, V and Zn) and nutrient (N, P, dissolved organic carbon) concentrations. The first rain sample collected in the Ionian Sea (Rain ION) was a typical regional background wet deposition event, whereas the second rain sample collected in the Algerian Basin (Rain FAST) was a Saharan dust wet deposition event. Even in the remote Med Sea, all background TM inputs presented an anthropogenic signature, except for Fe, Mn and Ti. The concentrations of TMs in the two rain samples were significantly lower compared to concentrations in rains collected at coastal sites reported in the literature, due to the decrease in anthropogenic emissions during the preceding decades. The atmospheric TM inputs were mainly dissolved forms, even in dusty Rain FAST. The TM stocks in the mixed layer (ML, 0–20 m) at the FAST station before and after the event showed that the atmospheric inputs were a significant supply of particulate TMs and dissolved Fe and Co for surface seawater. Even if the wet deposition delivers TMs mainly in soluble form, the post-deposition aerosol dissolution could to be a key additional pathway in the supply of dissolved TMs. At the scale of the western and central Mediterranean, the atmospheric inputs were of the same order of magnitude as ML stocks for dissolved Fe, Co and Zn, highlighting the role of the atmosphere in their biogeochemical cycles in the stratified Med Sea. In case of intense dust-rich wet deposition events, the role of atmospheric inputs as an external source was extended to dissolved Co, Fe, Mn, Pb and Zn. Our results suggest that the wet deposition constitutes only a source of some of dissolved TMs for Med Sea surface waters. The contribution of dry deposition to the atmospheric TM inputs needs to be investigated.
N2 fixation rates were measured in the 0–1000 m layer at 13 stations located in the open western and central Mediterranean Sea (MS) during the PEACETIME cruise (late spring 2017). While the spatial variability in N2 fixation was not related to Fe, P nor N stocks, the surface composition of the diazotrophic community indicated a strong longitudinal gradient increasing eastward for the relative abundance of non-cyanobacterial diazotrophs (NCDs) (mainly γ-Proteobacteria) and conversely decreasing eastward for photo-heterotrophic group A (UCYN-A) (mainly UCYN-A1 and UCYN-A3), as did N2 fixation rates. UCYN-A4 and UCYN-A3 were identified for the first time in the MS. The westernmost station influenced by Atlantic waters and characterized by highest stocks of N and P displayed a patchy distribution of diazotrophic activity with an exceptionally high rate in the euphotic layer of 72.1 nmolNL-1d-1, which could support up to 19 % of primary production. At this station at 1 % PAR (photosynthetically available radiation) depth, UCYN-A4 represented up to 94 % of the diazotrophic community. These in situ observations of greater relative abundance of UCYN-A at stations with higher nutrient concentrations and dominance of NCDs at more oligotrophic stations suggest that nutrient conditions – even in the nanomolar range – may determine the composition of diazotrophic communities and in turn N2 fixation rates. The impact of Saharan dust deposition on N2 fixation and diazotrophic communities was also investigated, under present and future projected conditions of temperature and pH during short-term (3–4 d) experiments at three stations. New nutrients from simulated dust deposition triggered a significant stimulation of N2 fixation (from 41 % to 565 %). The strongest increase in N2 fixation was observed at the stations dominated by NCDs and did not lead on this short timescale to changes in the diazotrophic community composition. Under projected future conditions, N2 fixation was either increased or unchanged; in that later case this was probably due to a too-low nutrient bioavailability or an increased grazing pressure. The future warming and acidification likely benefited NCDs (Pseudomonas) and UCYN-A2, while disadvantaged UCYN-A3 without knowing which effect (alone or in combination) is the driver, especially since we do not know the temperature optima of these species not yet cultivated as well as the effect of acidification.
Effective data management plays a key role in oceanographic research as cruise-based data, collected from different laboratories and expeditions, are commonly compiled to investigate regional to global oceanographic processes. Here we describe new and updated best practice data standards for discrete chemical oceanographic observations, specifically those dealing with column header abbreviations, quality control flags, missing value indicators, and standardized calculation of certain properties. These data standards have been developed with the goals of improving the current practices of the scientific community and promoting their international usage. These guidelines are intended to standardize data files for data sharing and submission into permanent archives. They will facilitate future quality control and synthesis efforts and lead to better data interpretation. In turn, this will promote research in ocean biogeochemistry, such as studies of carbon cycling and ocean acidification, on regional to global scales. These best practice standards are not mandatory. Agencies, institutes, universities, or research vessels can continue using different data standards if it is important for them to maintain historical consistency. However, it is hoped that they will be adopted as widely as possible to facilitate consistency and to achieve the goals stated above.
Mineral dust deposition is an important supply mechanism for trace elements in the low-latitude ocean. Our understanding of the controls of such inputs has been mostly built on laboratory and surface ocean studies. The lack of direct observations and the tendency to focus on near-surface waters prevent a comprehensive evaluation of the role of dust in oceanic biogeochemical cycles. In the frame of the PEACETIME project (ProcEss studies at the Air-sEa Interface after dust deposition in the MEditerranean sea), the responses of the aluminum (Al) and iron (Fe) cycles to two dust wet deposition events over the central and western Mediterranean Sea were investigated at a timescale of hours to days using a comprehensive dataset gathering dissolved and suspended particulate concentrations, along with sinking fluxes. Dissolved Al (dAl) removal was dominant over dAl released from dust. The Fe / Al ratio of suspended and sinking particles revealed that biogenic particles, and in particular diatoms, were key in accumulating and exporting Al relative to Fe. By combining these observations with published Al / Si ratios of diatoms, we show that adsorption onto biogenic particles, rather than active uptake, represents the main sink for dAl in Mediterranean waters. In contrast, systematic dissolved Fe (dFe) accumulation occurred in subsurface waters (∼ 100–1000 m), while dFe input from dust was only transient in the surface mixed layer. The rapid transfer of dust to depth, the Fe-binding ligand pool in excess to dFe in subsurface (while nearly saturated in surface), and low scavenging rates in this particle-poor depth horizon are all important drivers of this subsurface dFe enrichment. At the annual scale, this previously overlooked mechanism may represent an additional pathway of dFe supply for the surface ocean through diapycnal diffusion and vertical mixing. However, low subsurface dFe concentrations observed at the basin scale (
In the Gulf of Mexico (GoM), the upper 300 m of the water column contains a mixture of water types derived from water masses from the North Atlantic and the Caribbean Sea, namely Caribbean Surface Water (CSW), Subtropical Underwater (SUW), Gulf Common Water (GCW), and Tropical Atlantic Central Water (TACW). These are mainly altered by mesoscale processes and local evaporation, which modulate biogeochemical cycles. In this study, we improve our understanding of water mass dynamics by including biogeochemical data when evaluating the T-S relationship to define water-mass boundaries, particularly when the observed thermohaline characteristics overlap. The variables considered were apparent oxygen utilization (AOU), nitrate, and dissolved inorganic carbon (DIC). The data were obtained from eight cruises carried out in the central and southern regions of the GoM and an additional cruise that covered the entire coastal-ocean region. The new proposed boundaries were instrumental in clarifying the dynamics of surface waters. Of note, GCW on the western side of the GoM is not formed from the mixing of CSW and SUW but by the mixing of remnant CSW with TACW. In winter, a remnant of CSW mixed with GCW, and the biogeochemical composition of surface waters was affected, as observed from an increase in nitrate and DIC concentrations and positive AOU values. CSW was mainly detected at the surface during summer with negative AOU values, low DIC values, and almost undetectable nitrate concentrations. The presence or absence of CSW modulated the depth of the nitracline and likely influenced primary productivity.
Studying carbon dioxide in the ocean helps to understand how the ocean will be impacted by climate change and respond to increasing fossil fuel emissions. The marine carbonate system is not well characterized in the Arctic, where challenging logistics and extreme conditions limit observations of atmospheric CO2 flux and ocean acidification. Here, we present a high-resolution marine carbon system data set covering the complete cycle of sea-ice growth and melt in an Arctic estuary (Nunavut, Canada). This data set was collected through three consecutive yearlong deployments of sensors for pH and partial pressure of CO2 in seawater (pCO2sw) on a cabled underwater observatory. The sensors were remarkably stable compared to discrete samples: While corrections for offsets were required in some instances, we did not observe significant drift over the deployment periods. Our observations revealed a strong seasonality in this marine carbon system. Prior to sea-ice formation, air–sea gas exchange and respiration were the dominant processes, leading to increasing pCO2sw and reduced aragonite saturation state (ΩAr). During sea-ice growth, water column respiration and brine rejection (possibly enriched in dissolved inorganic carbon, relative to alkalinity, due to ikaite precipitation in sea ice) drove pCO2sw to supersaturation and lowered ΩAr to < 1. Shortly after polar sunrise, the ecosystem became net autotrophic, returning pCO2sw to undersaturation. The biological community responsible for this early switch to autotrophy (well before ice algae or phytoplankton blooms) requires further investigation. After sea-ice melt initiated, an under-ice phytoplankton bloom strongly reduced aqueous carbon (chlorophyll-a max of 2.4 µg L–1), returning ΩAr to > 1 after 4.5 months of undersaturation. Based on simple extrapolations of anthropogenic carbon inventories, we suspect that this seasonal undersaturation would not have occurred naturally. At ice breakup, the sensor platform recorded low pCO2sw (230 µatm), suggesting a strong CO2 sink during the open water season.
Estimating sea–air CO2 fluxes in coastal seas remains a source of uncertainty in global carbon budgets because processes like primary production, upwelling, water mixing, and freshwater inputs produce high spatial and temporal variability of CO2 partial pressure (pCO2). As a result, improving our pCO2 baseline observations in these regions is important, especially in sub-Arctic and Arctic seas that are experiencing strong impacts of climate change. Here, we show the patterns and main processes controlling seawater pCO2 and sea–air CO2 fluxes in Hudson Bay during the 2018 spring and early summer seasons. We observed spatially limited pCO2 supersaturation (relative to the atmosphere) near river mouths and beneath sea ice and widespread undersaturated pCO2 in offshore and ice-melt-influenced waters. pCO2 was highly correlated with salinity and temperature, with a limited but statistically significant relationship with chlorophyll a and fluorescent dissolved organic matter. Hudson Bay on average was undersaturated with respect to atmospheric CO2, which we attribute mainly to the dominance of sea-ice meltwater. We calculated an average net CO2 flux of about –5mmol CO2 m–2 day–1 (–3.3 Tg C) during the spring and early summer seasons (92 days). Combining this result with extrapolated estimates for late summer and fall seasons, we estimate the annual CO2 flux of Hudson Bay during the open water season (184 days) to be –7.2 Tg C. Our findings indicate that the bay on average is a weaker CO2 sink than most other Arctic seas, emphasizing the importance of properly accounting for seasonal variability in the Arctic coastal shelves to obtain reliable sea–air CO2 exchange budgets.
The ocean absorbs anthropogenic carbon, slowing atmospheric CO2 increase but driving ocean acidification. Long‐term changes in the carbon system are typically assessed from single‐point time series or from hydrographic sections spaced by decades. Using higher resolution observations (1–3 year⁻¹) from the Line P time series, we investigate processes modulating trends in the carbon system of the northeast subarctic Pacific. Dissolved inorganic carbon (DIC) and apparent oxygen utilization (AOU) from 1990 to 2019 reveal substantial trends over most of the upper water column along the 1,500 km coastal to open ocean transect. At the surface, an increasing trend in salinity‐normalized DIC (sDIC33) (+0.5 ± 0.4 μmol kg⁻¹ yr⁻¹) is associated with a decrease in pH (0.01–0.02 decade⁻¹) and a decrease in aragonite saturation state (0.04–0.08 decade⁻¹). These observed trends are driven by anthropogenic CO2 uptake, partially offset by trends in surface salinity or temperature. Stratification associated with recent marine heat waves appears to have caused anomalously low surface pCO2. sDIC33 trends of similar magnitude were found below the seasonal thermocline on the 26.7–26.8 isopycnals (150–300 m), which are ventilated in the western Pacific. Roughly, a third (20%–50%) of the subsurface sDIC33 trend is driven by increased remineralization, likely caused by long‐term decreases in ventilation in the western Pacific. Bidecadal oscillations in the ventilation of the 26.7–26.8 isopycnals arising from the Lunar Nodal Cycle cause oscillations in sDIC33 and AOU at the offshore end of our transect. We trace the oscillations to alternating periods of higher anthropogenic carbon uptake or higher carbon remineralization.
The surface mixed layer (ML) in the Mediterranean Sea is a well-stratified domain characterized by low macronutrients and low chlorophyll content for almost 6 months of the year. In this study we characterize the biogeochemical cycling of nitrogen (N) in the ML by analyzing simultaneous in situ measurements of atmospheric deposition, nutrients in seawater, hydrological conditions, primary production, heterotrophic prokaryotic production, N2 fixation and leucine aminopeptidase activity. Dry deposition was continuously measured across the central and western open Mediterranean Sea, and two wet deposition events were sampled, one in the Ionian Sea and one in the Algerian Basin. Along the transect, N budgets were computed to compare the sources and sinks of N in the mixed layer. In situ leucine aminopeptidase activity made up 14 % to 66 % of the heterotrophic prokaryotic N demand, and the N2 fixation rate represented 1 % to 4.5 % of the phytoplankton N demand. Dry atmospheric deposition of inorganic nitrogen, estimated from dry deposition of nitrate and ammonium in aerosols, was higher than the N2 fixation rates in the ML (on average 4.8-fold). The dry atmospheric input of inorganic N represented a highly variable proportion of biological N demand in the ML among the stations, 10 %–82 % for heterotrophic prokaryotes and 1 %–30 % for phytoplankton. As some sites were visited on several days, the evolution of biogeochemical properties in the ML and within the nutrient-depleted layers could be followed. At the Algerian Basin site, the biogeochemical consequences of a wet dust deposition event were monitored through high-frequency sampling. Notably, just after the rain, nitrate was higher in the ML than in the nutrient-depleted layer below. Estimates of nutrient transfer from the ML into the nutrient-depleted layer could explain up to a third of the nitrate loss from the ML. Phytoplankton did not benefit directly from the atmospheric inputs into the ML, probably due to high competition with heterotrophic prokaryotes, also limited by N and phosphorus (P) availability at the time of this study. Primary producers decreased their production after the rain but recovered their initial state of activity after a 2 d lag in the vicinity of the deep chlorophyll maximum layer.
Although atmospheric dust fluxes from arid as well as human-impacted areas represent a significant source of nutrients to surface waters of the Mediterranean Sea, studies focusing on the evolution of the metabolic balance of the plankton community following a dust deposition event are scarce, and none were conducted in the context of projected future levels of temperature and pH. Moreover, most of the experiments took place in coastal areas. In the framework of the PEACETIME project, three dust-addition perturbation experiments were conducted in 300 L tanks filled with surface seawater collected in the Tyrrhenian Sea (TYR), Ionian Sea (ION) and Algerian basin (FAST) on board the R/V Pourquoi Pas? in late spring 2017. For each experiment, six tanks were used to follow the evolution of chemical and biological stocks, biological activity and particle export. The impacts of a dust deposition event simulated at their surface were followed under present environmental conditions and under a realistic climate change scenario for 2100 (ca. +3 ∘C and −0.3 pH units). The tested waters were all typical of stratified oligotrophic conditions encountered in the open Mediterranean Sea at this period of the year, with low rates of primary production and a metabolic balance towards net heterotrophy. The release of nutrients after dust seeding had very contrasting impacts on the metabolism of the communities, depending on the station investigated. At TYR, the release of new nutrients was followed by a negative impact on both particulate and dissolved 14C-based production rates, while heterotrophic bacterial production strongly increased, driving the community to an even more heterotrophic state. At ION and FAST, the efficiency of organic matter export due to mineral/organic aggregation processes was lower than at TYR and likely related to a lower quantity/age of dissolved organic matter present at the time of the seeding and a smaller production of DOM following dust addition. This was also reflected by lower initial concentrations in transparent exopolymer particles (TEPs) and a lower increase in TEP concentrations following the dust addition, as compared to TYR. At ION and FAST, both the autotrophic and heterotrophic community benefited from dust addition, with a stronger relative increase in autotrophic processes observed at FAST. Our study showed that the potential positive impact of dust deposition on primary production depends on the initial composition and metabolic state of the investigated community. This impact is constrained by the quantity of nutrients added in order to sustain both the fast response of heterotrophic prokaryotes and the delayed one of primary producers. Finally, under future environmental conditions, heterotrophic metabolism was overall more impacted than primary production, with the consequence that all integrated net community production rates decreased with no detectable impact on carbon export, therefore reducing the capacity of surface waters to sequester anthropogenic CO2.
The budget of reactive nitrogen (Nr; oxidized and reduced inorganic and organic forms of nitrogen) has at least doubled since the preindustrial era due to human activities. There are significant detrimental effects of this excess Nr on many terrestrial and aquatic ecosystems, although less is known about the impact on the open ocean. Nr deposition may already rival biological N 2 fixation quantitatively and will likely continue to rise in the future. However, it is unclear how much of the Nr currently deposited to the ocean is external in origin. Understanding the importance of ocean Nr emissions versus external Nr deposition is key to quantifying the influence of deposition on ocean biogeochemistry and climate. This article reviews our understanding of the impacts of Nr deposition on the open ocean and the emissions of Nr from the ocean, placing particular emphasis on stable isotopes as a tool to investigate the surface ocean–lower atmosphere Nr cycle and its variations over time. ▪ The ocean has a dynamic exchange of reactive nitrogen with the atmosphere and is not just a passive recipient of nitrogen pollution from land. ▪ Tracing anthropogenic nitrogen deposition to the ocean is a challenge due to overlapping geochemical signatures with other nitrogen inputs. ▪ However, studies suggest an imprint of external (anthropogenic) nitrogen deposition in the Mediterranean Sea and North Pacific Ocean. ▪ Climate change will impact nitrogen emissions from the ocean through warming, acidification, stratification, and changes in food webs. Expected final online publication date for the Annual Review of Earth and Planetary Sciences, Volume 49 is May 2021. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.
Plain Language Summary Ammonia is the most important basic gas in the atmosphere and it plays an important role in forming new aerosols and controlling the acidity of aerosols, with implications for climate. Ammonia emissions to the atmosphere have increased significantly over time due to human activities, primarily related to agriculture. There are very few regions where one can observe the atmosphere away from these human emissions, making it difficult to quantify natural processes. Our study investigated ocean ammonia fluxes, which are thought to be the largest natural source of ammonia globally, across the Atlantic Southern Ocean where human influences should be minimal. Previous studies have suggested that in this region, the ammonia should flux into the ocean because of the cold surface seawater, but direct measurements are scarce. We found that the flux was indeed into the ocean across the latitudinal transect, although the values were small. A sensitivity analysis suggests that the flux could easily reverse as a result of seasonal changes in surface ocean biological and chemical processes. More observations are needed in this remote region of the atmosphere, particularly during the inhospitable winter season, in order to understand the natural cycling of ammonia between the ocean and atmosphere.
The atmospheric aerosol has a large influence on global climate through its ability of scattering and absorbing electromagnetic radiation, which affect the Earth's radiative balance. Characteristics, such as size distribution, chemical composition and hygroscopic properties are important for improving global climate model projections of natural sea spray aerosols, which are numerically dominant in the global aerosol budget. Previous experimental studies in coastal locations revealed a complex mixing between natural and anthropogenic aerosols. This complexity makes it difficult to characterize the behavior of natural sea spray aerosols in a simplified form that is suitable for global models. The aim of the present paper is to characterize the size distributions of natural sea spray aerosols at a coastal site in False Bay, South Africa. The opening of False Bay towards the Southern Ocean with unlimited fetch from Antarctica provides a unique opportunity to measure and focus on pristine marine air masses solely. A large observational data set from the First European-South African Transmission Experiment (FESTER) was analyzed and two case studies are presented to illustrate the contribution of sea spray to aerosol size distributions under pure marine and mixed air mass conditions, respectively. A set of conditions for measuring pure marine aerosols in False Bay was established. The results of the relationship of aerosol concentrations with wind speed reveals the distinct behavior of natural sea spray aerosols and demonstrates the pure marine influence of the Southern Ocean in False Bay. Comparison of the aerosol size distributions to a coastal site in the Mediterranean Sea, attest to the contribution of sea spray to aerosol size distributions in False Bay.
Plain‐Language summary Phytoplankton are microscopic organisms that live in watery environments such as the ocean. Like land plants, phytoplankton need nutrients to survive, develop, and reproduce. In the surface ocean, nutrients come from one of several pathways: from the depths of the ocean, from the rivers, and from the atmosphere. In the Arabian Sea, there are two important sources of nutrients for the organisms living in the surface layer of the ocean: the nutrient‐rich waters coming from below, which occurs along the coast of the Arabian Peninsula, and the desert dust deposited from above. In this study, we show that neither source brings all the necessary nutrients nor brings enough nutrients. Both of these types of inputs are required to understand the distribution of the phytoplankton. If there was no dust deposition in the Arabian Sea, these organisms that represent the first link in the ocean food chain would be half as abundant as they are currently.
The dissolved iron supply controls half of the oceans’ primary productivity. Resupply by the remineralization of sinking particles, and subsequent vertical mixing, largely sustains this productivity. However, our understanding of the drivers of dissolved iron resupply, and their influence on its vertical distribution across the oceans, is still limited due to sparse observations. There is a lack of empirical evidence as to what controls the subsurface iron remineralization due to difficulties in studying mesopelagic biogeochemistry. Here we present estimates of particulate transformations to dissolved iron, concurrent oxygen consumption and iron-binding ligand replenishment based on in situ mesopelagic experiments. Dissolved iron regeneration efficiencies (that is, replenishment over oxygen consumption) were 10- to 100-fold higher in low-dust subantarctic waters relative to higher-dust Mediterranean sites. Regeneration efficiencies are heavily influenced by particle composition. Their make-up dictates ligand release, controls scavenging, modulates ballasting and may lead to the differential remineralization of biogenic versus lithogenic iron. At high-dust sites, these processes together increase the iron remineralization length scale. Modelling reveals that in oceanic regions near deserts, enhanced lithogenic fluxes deepen the ferricline, which alter the vertical patterns of dissolved iron replenishment, and set its redistribution at the global scale. Such wide-ranging regeneration efficiencies drive different vertical patterns in dissolved iron replenishment across oceanic provinces.
The Sea Surface Microlayer (SML) is known to be enriched by trace metals relative to the underlying water and harbor diverse microbial communities (i.e., neuston). However, the processes linking metals and biota in the SML are not yet fully understood. The metal (Cd, Co, Cu, Fe, Ni, Mo, V, Zn and Pb) concentrations in aerosol samples in the SML (dissolved and total fractions) and in subsurface waters (SSWs; dissolved fraction at ∼1 m depth) from the western Mediterranean Sea were analyzed in this study during a cruise in May–June 2017. The composition and abundance of the bacterial community in the SML and SSW, the primary production, and Chl a in the SSW were measured simultaneously at all stations during the cruise. Residence times in the SML of metals derived from aerosol depositions were highly variable and ranged from minutes for Fe (3.6±6.0 min) to a few hours for Cu (5.8±6.2 h). Concentrations of most of the dissolved metals in both the SML and SSW were positively correlated with the salinity gradient and showed the characteristic eastward increase in the surface waters of the Mediterranean Sea (MS). In contrast, the total fraction of some reactive metals in the SML (i.e., Cu, Fe, Pb and Zn) showed a negative correlation with salinity and a positive correlation with microbial abundance, which might be associated with microbial uptake. Our results show a strong negative correlation between the dissolved and total Ni concentration and heterotrophic bacterial abundance in the SML and SSW, but we cannot ascertain whether this correlation reflects a toxicity effect or is the result of some other process.
In surface waters from the Southern Ocean and from the west coast of Baja California, a relationship was found between pH and water column density. In the Southern Ocean, pH was found to correlate well with density and salinity but not with temperature because water column stability was due to salinity. The opposite was found on the west coast of Baja California, where density was controlled by temperature. This demonstrates that pH follows density independently of what controls it. According to the results of this work, we suggest that pH-density correlations may be an important option in the development of algorithms for monitoring CO2 from satellite imagery.
This study reports the potential contribution of organic bases to the alkalinity of seawater samples. The concentration of organic bases in these samples was inferred from the difference between the measured alkalinity and that calculated from a knowledge of pH and concentrations of the various inorganic acid-bases species such as total carbon, total boron, and so on. Significant concentrations of such organic bases were measured in cultures of the marine microalgae Rhodomonas sp. (800 µmol kg−1) and Isochrysis aff. Galbana (400 µmol kg−1), as well as in three marine environments (northern gulf of California, México; San Quintín Bay, B.C., Mexico; and San Diego Bay). These three sites are characterized by significant biological activity and restricted mixing, and the organic bases were found at concentrations greater than 50 µmol kg−1 in each of these three locations.
The temporal and spatial variability of dissolved inorganic phosphate (DIP), nitrogen (DIN), carbon (DIC) and dissolved organic carbon (DOC) were studied in order to determine the net ecosystem metabolism (NEM) of San Diego Bay (SDB), a Mediterranean-climate lagoon. A series of four sampling campaigns were carried out during the rainy (January 2000) and the dry (August 2000 and May and September 2001) seasons. During the dry season, temperature, salinity and DIP, DIC and DOC concentrations increased from oceanic values in the outer bay to higher values at the innermost end of the bay. DIP, DIC and DOC concentrations showed a clear offset from conservative mixing implying production of these dissolved materials inside the bay. During the rainy season, DIP and DOC increased to the head, whereas salinity decreased toward the mouth due to land runoff and river discharges. The distributions of DIP and DOC also showed a deviation from conservative mixing in this season, implying a net addition of these dissolved materials during estuarine mixing within the bay. Mass balance calculations showed that SDB consistently exported DIP (2.8e9.8 Â 10 3 mol P d À1), DIC (263e352 Â 10 3 mol C d À1) and DOC (198e1233 Â 10 3 mol C d À1), whereas DIN (5.5e18.2 Â 10 3 mol N d À1) was exported in all samplings except in May 2001 when it was imported (8.6 Â 10 3 mol N d À1). The DIP, DIC and DOC export rates along with the strong relationship between DIP, DIC or DOC and salinity suggest that intense tidal mixing plays an important role in controlling their distributions and that SDB is a source of nutrients and DOC to the Southern California Bight. Fur-thermore, NEM ranged from À8.1 AE 1.8 mmol C m À2 d À1 in September to À13.5 AE 5.8 mmol C m À2 d À1 in January, highlighting the heterotro-phic character of SDB. In order to explain the net heterotrophy of this system, we postulate that phytoplankton-derived particulate organic matter, stimulated by upwelling processes in the adjacent coastal waters, is transported into the bay, retained and then remineralized within the system. Our results were compared with those reported for the heterotrophic hypersaline coastal lagoons located in the semi-arid coast of CaliforniaeBaja California, and with those autotrophic hypersaline systems found in the semi-arid areas of Australia. We point out that the balance between autotrophy and heterotrophy in inverse estuaries is dependent on net external inputs of either inorganic nutrients or organic matter as it has been indicated for positive estuaries.
The study of long-term trends in aerosol optical properties is an important task to understand the underlying aerosol processes influencing the change of climate. The Arctic, as the place where climate change manifests most, is an especially sensitive region of the world. Within this work, we use a unique long-term data record of key aerosol optical properties from the Zeppelin Observatory, Svalbard, to ask the question of whether the environmental changes of the last 2 decades in the Arctic are reflected in the observations. We perform a trend analysis of the measured particle light scattering and backscattering coefficients and the derived scattering Ångstrom exponent and hemispheric backscattering fraction. In contrast to previous studies, the effect of in-cloud scavenging and of potential sampling losses at the site are taken explicitly into account in the trend analysis. The analysis is combined with a back trajectory analysis and satellite-derived sea ice data to support the interpretation of the observed trends. We find that the optical properties of aerosol particles have undergone clear and significant changes in the past 2 decades. The scattering Ångstrom exponent exhibits statistically significant decreasing of between -4.9%yr-1 and -6.5%yr-1 (using wavelengths of λ= 450 and 550 nm), while the particle light scattering coefficient exhibits statistically significant increasing trends of between 2.6%yr-1 and 2.9%yr-1 (at a wavelength of λ = 550 nm). The magnitudes of the trends vary depending on the season. These trends indicate a shift to an aerosol dominated more by coarse-mode particles, most likely the result of increases in the relative amount of sea spray aerosol. We show that changes in air mass circulation patterns, specifically an increase in air masses from the south-west, are responsible for the shift in aerosol optical properties, while the decrease of Arctic sea ice in the last 2 decades only had a marginal influence on the observed trends.
We have developed an inorganic sea spray source function that is based upon state-of-the-art measurements of sea spray aerosol production using a temperature-controlled plunging jet sea spray aerosol chamber. The size-resolved particle production was measured between 0.01 and 10 μm dry diameter. Particle production decreased non-linearly with increasing seawater temperature (between −1 and 30 °C) similar to previous findings. In addition, we observed that the particle effective radius, as well as the particle surface, particle volume and particle mass, increased with increasing seawater temperature due to increased production of particles with dry diameters greater than 1 μm. By combining these measurements with the volume of air entrained by the plunging jet we have determined the size-resolved particle flux as a function of air entrainment. Through the use of existing parameterisations of air entrainment as a function of wind speed, we were subsequently able to scale our laboratory measurements of particle production to wind speed. By scaling in this way we avoid some of the difficulties associated with defining the "white area" of the laboratory whitecap – a contentious issue when relating laboratory measurements of particle production to oceanic whitecaps using the more frequently applied whitecap method. The here-derived inorganic sea spray source function was implemented in a Lagrangian particle dispersion model (FLEXPART – FLEXible PARTicle dispersion model). An estimated annual global flux of inorganic sea spray aerosol of 5.9 ± 0.2 Pg yr−1 was derived that is close to the median of estimates from the same model using a wide range of existing sea spray source functions. When using the source function derived here, the model also showed good skill in predicting measurements of Na+ concentration at a number of field sites further underlining the validity of our source function. In a final step, the sensitivity of a large-scale model (NorESM – the Norwegian Earth System Model) to our new source function was tested. Compared to the previously implemented parameterisation, a clear decrease of sea spray aerosol number flux and increase in aerosol residence time was observed, especially over the Southern Ocean. At the same time an increase in aerosol optical depth due to an increase in the number of particles with optically relevant sizes was found. That there were noticeable regional differences may have important implications for aerosol optical properties and number concentrations, subsequently also affecting the indirect radiative forcing by non-sea spray anthropogenic aerosols.
In the central Arctic Ocean the formation of clouds and their properties are sensitive to the availability of cloud condensation nuclei (CCN). The vapors responsible for new particle formation (NPF), potentially leading to CCN, have remained unidentified since the first aerosol measurements in 1991. Here, we report that all the observed NPF events from the Arctic Ocean 2018 expedition are driven by iodic acid with little contribution from sulfuric acid. Iodic acid largely explains the growth of ultrafine particles (UFP) in most events. The iodic acid concentration increases significantly from summer towards autumn, possibly linked to the ocean freeze-up and a seasonal rise in ozone. This leads to a one order of magnitude higher UFP concentration in autumn. Measurements of cloud residuals suggest that particles smaller than 30 nm in diameter can activate as CCN. Therefore, iodine NPF has the potential to influence cloud properties over the Arctic Ocean.
Understanding the physical and biogeochemical interactions and feedbacks between the ocean and atmosphere is a vital component of environmental and Earth system research. The ability to predict and respond to future environmental change relies on a detailed understanding of these processes. The Surface Ocean-Lower Atmosphere Study (SOLAS) is an international research platform that focuses on the study of ocean-atmosphere interactions, for which Future Earth is a sponsor. SOLAS instigated a collaborative initiative process to connect efforts in the natural and social sciences related to these processes, as a contribution to the emerging Future Earth Ocean Knowledge-Action Network (Ocean KAN). This is imperative because many of the recent changes in the Earth system are anthropogenic. An understanding of adaptation and counteracting measures requires an alliance of scientists from both domains to bridge the gap between science and policy. To this end, three SOLAS research areas were targeted for a case study to determine a more effective method of interdisciplinary research: valuing carbon KEYWORDS Air-sea interactions; policy across the air-sea interface; shipping and biogeochemistry; social science; SOLAS science and society; valuing ocean carbon and the ocean's role; air-sea interactions, policy and stewardship; and, air-sea interactions and the shipping industry.
One of the most important breakthroughs in oceanography in the last 30 years was the discovery that iron (Fe) controls biological production as a micronutrient, and our understanding of Fe and nutrient biogeochemical dynamics in the ocean has significantly advanced. In this review, we looked back both previous and updated knowledge of the natural Fe supply processes and nutrient dynamics in the subarctic Pacific and its impact on biological production. Although atmospheric dust has been considered to be the most important source of Fe affecting biological production in the subarctic Pacific, other oceanic sources of Fe have been discovered. We propose a coherent explanation for the biological response in subarctic Pacific high nutrient low chlorophyll (HNLC) waters that incorporates knowledge of both the atmospheric Fe supplies and the oceanic Fe supplies. Finally, we extract future directions for Fe oceanographic research in the subarctic Pacific and summarize the uncertain issues identified thus far.
The objective of this study was to assess experimentally the potential impact of anthropogenic pH perturbation (ApHP) on concentrations of dimethyl sulfide (DMS) and dimethylsulfoniopropionate (DMSP), as well as processes governing the microbial cycling of sulfur compounds. A summer planktonic community from surface waters of the Lower St. Lawrence Estuary was monitored in microcosms over 12 days under three pCO2 targets: 1 × pCO2 (775 µatm), 2 × pCO2 (1,850 µatm), and 3 × pCO2 (2,700 µatm). A mixed phytoplankton bloom comprised of diatoms and unidentified flagellates developed over the course of the experiment. The magnitude and timing of biomass buildup, measured by chlorophyll a concentration, changed in the 3 × pCO2 treatment, reaching about half the peak chlorophyll a concentration measured in the 1 × pCO2 treatment, with a 2-day lag. Doubling and tripling the pCO2 resulted in a 15% and 40% decline in average concentrations of DMS compared to the control. Results from 35S-DMSPd uptake assays indicated that neither concentrations nor microbial scavenging efficiency of dissolved DMSP was affected by increased pCO2. However, our results show a reduction of the mean microbial yield of DMS by 34% and 61% in the 2 × pCO2 and 3 × pCO2 treatments, respectively. DMS concentrations correlated positively with microbial yields of DMS (Spearman’s ρ = 0.65; P < 0.001), suggesting that the impact of ApHP on concentrations of DMS in diatom-dominated systems may be strongly linked with alterations of the microbial breakdown of dissolved DMSP. Findings from this study provide further empirical evidence of the sensitivity of the microbial DMSP switch under ApHP. Because even small modifications in microbial regulatory mechanisms of DMSP can elicit changes in atmospheric chemistry via dampened efflux of DMS, results from this study may contribute to a better comprehension of Earth’s future climate.
Iodine chemistry has noteworthy impacts on the oxidising capacity of the marine boundary layer (MBL) through the depletion of ozone (O3) and changes to HOx (OH∕HO2) and NOx (NO∕NO2) ratios. Hitherto, studies have shown that the reaction of atmospheric O3 with surface seawater iodide (I−) contributes to the flux of iodine species into the MBL mainly as hypoiodous acid (HOI) and molecular iodine (I2). Here, we present the first concomitant observations of iodine oxide (IO), O3 in the gas phase, and sea surface iodide concentrations. The results from three field campaigns in the Indian Ocean and the Southern Ocean during 2015–2017 are used to compute reactive iodine fluxes in the MBL. Observations of atmospheric IO by multi-axis differential optical absorption spectroscopy (MAX-DOAS) show active iodine chemistry in this environment, with IO values up to 1 pptv (parts per trillion by volume) below latitudes of 40∘ S. In order to compute the sea-to-air iodine flux supporting this chemistry, we compare previously established global sea surface iodide parameterisations with new region-specific parameterisations based on the new iodide observations. This study shows that regional changes in salinity and sea surface temperature play a role in surface seawater iodide estimation. Sea–air fluxes of HOI and I2, calculated from the atmospheric ozone and seawater iodide concentrations (observed and predicted), failed to adequately explain the detected IO in this region. This discrepancy highlights the need to measure direct fluxes of inorganic and organic iodine species in the marine environment. Amongst other potential drivers of reactive iodine chemistry investigated, chlorophyll a showed a significant correlation with atmospheric IO (R=0.7 above the 99 % significance level) to the north of the polar front. This correlation might be indicative of a biogenic control on iodine sources in this region.
Abstract. Iodine chemistry has noteworthysignificant impacts on the oxidising capacity of the marine boundary layer (MBL) through the depletion of ozone (O<sub>3</sub>) and changes to HO<sub>x</sub> (OH/HO<sub>2</sub>) and NO<sub>x</sub> (NO/NO<sub>2</sub>) ratios. Hitherto, studies have shown that the reaction of atmospheric O<sub>3</sub> with surface seawater iodide (I<sup>−</sup>) contributes to the flux of iodine species into the MBL mainly as hypoiodous acid (HOI) and molecular iodine (I<sub>2</sub>). Here, we present the first concomitant observations of iodine oxide (IO), O<sub>3</sub> in the gas phase, and sea surface iodide concentrations. The results from three field campaigns in the Indian Ocean and the Southern Ocean during 2014–2017 are used to compute reactive iodine fluxes to the MBL. Observations of atmospheric IO by MAX-DOAS show active iodine chemistry in this environment, with IO values up to 1 pptv (parts per trillion by volume) below latitudes of 40° S. In order to compute the sea-to-air iodine flux supporting this chemistry, we compare previously established global sea surface iodide parameterisations with new, region-specific parameterisations based on the new iodide observations. This study shows that regional changes in salinity and sea surface temperature play a role in surface seawater iodide estimation. Sea-air fluxes of HOI and I<sub>2</sub>, calculated from the atmospheric ozone and seawater iodide concentrations (observed and predicted), failed to adequately explain the detected IO in this region. This discrepancy highlights the need to measure direct fluxes of inorganic and organic iodine species in the marine environment. Amongst other potential drivers of reactive iodine chemistry investigated, chlorophyll- a showed a significant correlation with atmospheric IO (R = 0.7 above the 99 % significance level) to the north of the polar front. This correlation might be indicative of a biogenic control on iodine sources in this region.
Ocean-going ships supply products from one region to another and contribute to the world's economy. Ship exhaust contains many air pollutants and results in significant changes in marine atmospheric composition. The role of reactive halogen species (RHS) in the troposphere has received increasing recognition and oceans are the largest contributors to their atmospheric burden. However, the impact of shipping emissions on RHS and that of RHS on ship-originated air pollutants have not been studied in detail. Here, an updated Weather Research Forecasting coupled with Chemistry model is utilized to explore the chemical interactions between ship emissions and oceanic RHS over the East Asia seas in summer. The emissions and resulting chemical transformations from shipping activities increase the level of NO and NO2 at the surface, increase O3 in the South China Sea, but decrease O3 in the East China Sea. Such changes in pollutants result in remarkable changes in the levels of RHS (>200% increase of chlorine; ∼30% and ∼5% decrease of bromine and iodine, respectively) as well as in their partitioning. The abundant RHS, in turn, reshape the loadings of air pollutants (∼20% decrease of NO and NO2; ∼15% decrease of O3) and those of the oxidants (>10% reduction of OH and HO2; ∼40% decrease of NO3) with marked patterns along the ship tracks. We, therefore, suggest that these important chemical interactions of ship-originated emissions with RHS should be considered in the environmental policy assessments of the role of shipping emissions in air quality and climate.
Ice nucleating particles (INPs) in the atmosphere are necessary to generate ice crystals in mixed-phase clouds, a crucial component for precipitation development. The sources and composition of INPs are varied: from mineral dust derived from continental erosion to bioaerosols resulting from bubble bursting at the ocean surface. The performance of a home-built droplet freezing assay (DFA) device for quantifying the ice nucleating abilities of water samples via immersion freezing has been validated against both published results and analyses of samples from sea surface microlayer (SML) and bulk surface water (BSW) from the Gulf of Mexico (GoM) and Saanich Inlet, off Vancouver Island (VI), Canada. Even in the absence of phytoplankton blooms, all the samples contained INPs at moderate concentrations, ranging from 6.0x10^1 to 1.1x10^5 L-1 water. The freezing temperatures (i.e., T50, the temperature at which 50% of the droplets freeze) of the samples decreased in order of VI SML > GoM BSW > GoM SML, indicating that the higher latitude coastal waters have a greater potential to initiate cloud formation and precipitation.
Geoengineering strategies to slow sea ice melting would affect not only Earth's climate but also the biology and chemistry of the oceans, atmosphere, and ice.
We are developing a ship-based system to measure the air-sea pCO2 gradient and air-sea turbulent flux of CO2 over the ocean. The eddy covariance flux system uses off-the-shelf instruments to measure the turbulent wind vector (Campbell Scientific CSAT3 sonic anemometer), platform motion (Systron Donner Motion Pak II), and carbon dioxide molar density (LiCor 7000 Infrared Gas Analyzer). Two major sources of uncertainty in calculated fluxes are the effect of water vapor fluctuations on air density fluctuations (the WPL effect, Webb, Pearman and Leuning. 1980), and a spurious CO2 signal due to the sensitivity of the gas analyzer to platform motion (McGillis et al., 1998). Two flux systems were deployed side-by-side on a cruise from Manzanillo, Mexico to Puntas Arenas, Chile, in January 2006. Results from the cruise are presented, with a focus on our attempts to reduce biases in the calculated air-sea CO2 flux due to the WPL effect and the motion sensitivity of the gas analyzer.
Carbonyl sulfide (OCS) and carbon disulfide (CS2) are volatile sulfur gases that are naturally formed in seawater and exchanged with the atmosphere. OCS is the most abundant sulfur gas in the atmosphere, and CS2 is its most important precursor. They have attracted increased interest due to their direct (OCS) or indirect (CS2 via oxidation to OCS) contribution to the stratospheric sulfate aerosol layer. Furthermore, OCS serves as a proxy to constrain terrestrial CO2 uptake by vegetation. Oceanic emissions of both gases contribute a major part to their atmospheric concentration. Here we present a database of previously published and unpublished (mainly shipborne) measurements in seawater and the marine boundary layer for both gases, available at https://doi.org/10.1594/PANGAEA.905430 (Lennartz et al., 2019). The database contains original measurements as well as data digitalized from figures in publications from 42 measurement campaigns, i.e., cruises or time series stations, ranging from 1982 to 2019. OCS data cover all ocean basins except for the Arctic Ocean, as well as all months of the year, while the CS2 dataset shows large gaps in spatial and temporal coverage. Concentrations are consistent across different sampling and analysis techniques for OCS. The database is intended to support the identification of global spatial and temporal patterns and to facilitate the evaluation of model simulations.
Carbonyl sulfide (OCS) is the most abundant, long-lived sulphur gas in the atmosphere and a major supplier of sulfur to the stratospheric sulfate aerosol layer. The short-lived gas carbon disulfide (CS2) is oxidized to OCS and constitutes a major indirect source to the atmospheric OCS budget. The atmospheric budget of OCS is not well constrained due to a large missing source needed to compensate for substantial evidence that was provided for significantly higher sinks. Oceanic emissions are associated with major uncertainties. Here we provide a first, monthly resolved ocean emission inventory of both gases for the period 2000–2019 (available at https://doi.org/10.5281/zenodo.4297010) (Lennartz et al., 2020a). Emissions are calculated with a numerical box model (resolution 2.8° × 2.8° at equator, T42 grid) for the surface mixed layer. We find that interannual variability in OCS emissions is smaller than seasonal variability, and is mainly driven by variations in chromophoric dissolved organic matter (CDOM), which influences both photochemical and light-independent production. A comparison with a global database of more than 2500 measurements reveals overall good agreement. Emissions of CS2 constitute a larger sulfur source to the atmosphere than OCS, and equally show interannual variability connected to variability of CDOM. The emission estimate of CS2 is associated with higher uncertainties, as process understanding of the marine cycling of CS2 is incomplete. We encourage the use of the data provided here as input for atmospheric modelling studies to further assess the atmospheric OCS budget and the role of OCS in climate.
The ways in which marine biological activity affects climate, by modifying aerosol properties, are not completely understood, causing high uncertainties in climate predictions. In this work, in‐situ measurements of aerosol chemical composition, particle number size distribution, cloud condensation nuclei (CCN) and ice nucleating particle (INP) number concentrations are combined with high‐resolution sea surface chlorophyll‐a concentration (CHL) and back‐trajectory data to elucidate the relationship between oceanic biological activity and marine aerosol. The measurements were performed during an intensive field campaign conducted in late summer (August‐September) 2015 at the Mace Head Research Station (MHD). At the short time scale (1‐2 months) of the experiment, we observed a clear dependency of the main aerosol physico‐chemical and cloud‐relevant properties on the patterns of biological activity, in specific oceanic regions with a delayed response of about 1‐3 weeks. The oceanic region comprised between 47°−57° N and 14°−30° W was identified as the main source of biogenic aerosols during the campaign, with hints of some minor influence of waters up to the Greenland coast. These spatial and temporal relationships demonstrate that the marine biota influences aerosol properties under a variety of features up to the most cloud‐relevant properties. Such dependency of aerosol properties with oceanic biological activity was previously reported over the North Atlantic Ocean only for multi‐year datasets, where the correlation may be enhanced by coincident seasonalities. A better knowledge of these short time‐scale interactions may lead to a significant improvement in understanding the ocean‐atmosphere‐cloud system, with important impacts on climate science.
We present an aerosol cloud condensation nuclei (CCN) closure study over the Northeast Atlantic Ocean using six approximating methods. The CCN number concentrations (NCCN) were measured at four discrete super-saturations (SS, 0.25, 0.5, 0.75 and 1.0 %). Concurrently, aerosol number size distribution, sub-saturation hygroscopic growth factor and bulk PM1 chemical composition were obtained at matching time resolution and after a careful data validation exercise. Method A used a constant bulk hygroscopicity parameter κ of 0.3; method B used bulk PM1 chemical composition measured by an aerosol mass spectrometer (AMS); method C and D utilized a single size (165 nm) growth factor (GF) measured by humidified tandem differential mobility analyzer (HTDMA); method C utilized size-dependent GFs measured at 35, 50, 75, 110 and 165 nm; method E divided the aerosol population into three hygroscopicity modes (near-hydrophobic, more-hygroscopic and sea-salt modes) and the total CCN number in each mode was cumulatively added up; method F used the full size scale GF probability density function (GF-PDF) in the most complex approach. The studied periods included high biological activity and low biological activity seasons in clean marine and polluted continental air masses to represent and discuss the most contrasting aerosol populations. Overall, a good agreement was found between estimated and measured NCCN with a linear regression slopes ranging from 0.64 and 1.6. The temporal variability was captured very well with Pearson's R value ranging from 0.76 to 0.98 depending on the method and air mass type. We further compared the results of using different methods to quantify the impact of size-dependent hygroscopicity and mixing state and found that ignoring size-dependent hygroscopicity induced overestimation of NCCN by up to 12 %, and ignoring a mixing state induced overestimation of NCCN by up to 15 %. The error induced by assuming an internal mixing in highly polluted cases was largely eliminated by dividing the full GF-PDf into three conventional hygroscopic modes while assuming an internal mixing in clean marine aerosol did not induced significant error.
Many efforts have been dedicated toward understanding the role of biogenic sulfur particles as a climate regulator. Herein, we investigate the relationship between the atmospheric concentration of methanesulfonic acid (MSA) and phytoplankton biomass in the Mediterranean Sea by identifying the main MSA source regions during a springtime intensive observation period. The study approach combines i) spatio-temporal correlation analysis between in situ aerosol data measured in April 2016 at Capo Granitola (southern Sicily), and high-resolution ocean color composites, ii) back-trajectory analysis, and iii) potential source contribution function (PSCF) algorithm. The southwestern Mediterranean region (between Sardinia and the Algerian coast) was identified as the most probable dimethylsulfide (DMS) source region contributing to the observed MSA concentrations. Conversely, the blooming northwestern Mediterranean Sea region did not appear to contribute significantly. The present analysis shows that the reasons may be biotic (phytoplankton type, stress level) or abiotic (sea surface temperature), or a combination of both. We also postulate that the identified source region is associated with the production of non-sea-salt-sulfate and secondary organic aerosols from the processing of sea-released volatile organic compounds.
1] Satellite chlorophyll a (Chl a) concentrations and estimated primary production in the coastal seas of China were correlated with Asian dust events during 1998–2008. Dust events were identified using two approaches, i.e., historical record and satellite aerosol index (AI). Severe and very severe dust events correlated well and positively with Chl a concentrations and primary production in the south Yellow Sea and East China Sea, but it was not statistically significant in the Bohai Sea and the north Yellow Sea. In the south Yellow Sea, Chl a concentration and primary production increased and eventually bloomed 1–21 days after the occurrence of the 16 out of 22 dust storms. Granger causality test showed that AI, photosynthetically available radiation (PAR) and sea surface temperature (SST) did Granger cause primary production in the Yellow Sea, suggesting that past values of the above three variables contain statistically meaningful information about current values of primary production. A stepwise multiple linear regression was used to examine the relative importance of the three factors. PAR and SST accounted for most of the variability of primary production in the north Yellow Sea, while AI was not quite as useful. In the south Yellow Sea, PAR and AI accounted for most of the variability of primary production for all storms; in addition, spring algae blooms were due to dust particles transported in the <3 km layer of the atmosphere which passed through the loess plateau and/or megacities, while the higher‐level (>5 km) dusts, originated mainly from the Taklimakan Desert, Mongolia, and/or west of Inner Mongolia, had no impact.
Atmospheric deposition can deliver new nutrients to the surface water and support primary productivity. Here we report a phytoplankton bloom that developed in the Yellow Sea in the spring of 2007 3-4 days following a dust storm accompanied by precipitation. Our data indicate that atmospheric deposition dominated the supply of new nutrients to the surface water in the central Yellow Sea during the dust event. Dust-derived nitrogen (N) supply was sufficient to support the observed phytoplankton growth, while, dust-derived iron (Fe) supply far exceeded that required by the biota. Granger causality test results further supported that dust-derived nutrients deposition was the cause for the observed bloom with a lag of 3-5 days. Our results contribute to the growing database linking phytoplankton blooms to atmospheric deposition derived fertilization effects. Both dry and wet deposition contributed nutrients to the surface ocean during this event; however, the nutrient loading from dry deposition alone was not sufficient to satisfy the demand of the phytoplankton in this bloom event.
Organic nitrogen is a quantitatively important component of fixed nitrogen in atmospheric aerosol and rainwater. Urea as a possible candidate of organic nitrogen component might have a significant influence to the marine ecosystem since its bioavailability and broad range of natural and anthropogenic sources. 23 total suspended particulate samples, 4 size-segregated particles samples and 10 rainwater samples collected over the East China Sea from Nov. to Dec., 2006 and Feb. to Mar., 2007 were applied to analyze the concentrations of urea, nitrate and ammonium in aerosols and rainwater, respectively. In winter and spring, the concentrations of urea nitrogen were from 0.2 nmol m(-3) to 17.7 nmolx m(-3) and 6.5 nmol x m(-3) to 14.6 nmol x m(-3) in bulk aerosols, respectively and the corresponding concentrations were from 7.8 miromol x L(-1) to 18.1 micromol x L(-1) and 12.1 micromol x L(-1) to 35.3 micromol x L(-1) in rainwater. In both aerosols and rainwater over the East China Sea, the concentrations of urea nitrogen were higher in spring than those in winter. Urea nitrogen in aerosols contributed about 5% to the three measured nitrogen species and it was about 20% in rainwater. The size distribution of urea was markedly different from those of nitrate and ammonium,which had no pronounced difference among cascade stages. A slightly enhance urea contribution presented in the range of 0.43-0.65 microm in spring, which was 19.8%. In contrast, an enhancement presented in the range of 3.3-4.7 microm in winter, which was 19.8%. Factor analysis indicated that the sources of urea in aerosols were dominated by wind-blown soils in winter and sublime of urea in soils in spring, respectively.
Environmental context. Dimethylsulfide (DMS) is recognised as a potentially significant climate-forcing gas, owing to its role in particle and cloud formation in the marine atmosphere, where it is the dominant source of acidity. Ammonia, the dominant naturally occurring base in the atmosphere, plays an important role in neutralising particles formed from DMS oxidation products and may even enhance the formation rate of new particles. A biogeochemical coupling has previously been proposed between DMS and ammonia fluxes from the ocean to the atmosphere, in the form of coproduction of the two gases in seawater. We revise this suggestion by introducing the concept of ‘co-emission’ of the gases, where DMS emission controls the rate of emission of ammonia from the ocean by acidifying the atmosphere. Abstract. A strong correlation between aerosol ammonium and non-sea salt sulfate is commonly observed in the remote marine boundary layer. It has been suggested that this relationship implies a biogeochemical linkage between the nitrogen (N) and sulfur (S) cycles at the cellular biochemical level in phytoplankton in the ocean, or a linkage in the atmosphere (see P. S. Liss and J. N. Galloway, Interactions of C, N, P and S biogeochemical cycles and global change (Springer, 1993), and P. K. Quinn et al. in J. Geophys. Res. – Atmos. 1990, 95). We argue that an oceanic linkage is unlikely and draw on mechanistic and observational evidence to make the argument that the atmospheric connection is based on simple physical chemistry. Drawing on an established analogous concept in terrestrial trace gas biogeochemistry, we propose that any emission of dimethylsulfide (DMS) from the ocean will indirectly influence the flux of NH3 from the ocean, through the neutralisation of acidic DMS oxidation products and consequent lowering of the partial pressure of NH3 in the atmosphere. We present a simple numerical model to investigate this hypothesised phenomenon, using a parameterisation of the rate and thermodynamics of gas-to-particle conversion of NHx and explicitly modelled ocean–atmosphere NH3 exchange. The model indicates that emission of acidic sulfur to the atmosphere (e.g. as a product of DMS oxidation) may enhance the marine emission of NH3. It also suggests that the ratio of ammonium to non-sea salt sulfate in the aerosol phase is strongly dependent on seawater pH, temperature and wind speed – factors that control the ocean–atmosphere ammonia flux. Therefore, it is not necessary to invoke a stoichiometric link between production rates of DMS and ammonia in the ocean to explain a given ammonium to non-sea salt sulfate ratio in the aerosol. We speculate that this mechanism, which can provide a continuous resupply of ammonia to the atmosphere, may be involved in a series of biogeochemical-climate feedbacks.
Very short-lived halocarbons are significant sources of reactive halogen in the marine boundary layer, and likely in the upper troposphere and lower stratosphere. Quantifying ambient concentrations in the surface ocean and atmosphere is essential for understanding the atmospheric impact of these trace gas fluxes. Despite the body of literature increasing substantially over recent years, calibration issues complicate the comparison of results and limit the utility of building larger-scale databases that would enable further development of the science (e.g. sea-air flux quantification, model validation, etc.). With this in mind, thirty-one scientists from both atmospheric and oceanic halocarbon communities in eight nations gathered in London in February 2008 to discuss the scientific issues and plan an international effort toward developing common calibration scales ( http://tinyurl.com/c9cg58 ). Here, we discuss the outputs from this meeting, suggest the compounds that should be targeted initially, identify opportunities for beginning calibration and comparison efforts, and make recommendations for ways to improve the comparability of previous and future measurements.
We present an extensive data set of dimethylsulphide (DMS, n = 651) and dimethylsulphoniopropionate (DMSP, n = 590) from the Atlantic Meridional Transect program. These data are used to derive representative depth profiles that illustrate observed natural variations and can be used for DMS and DMSP model‐validation in oligotrophic waters. To further understand our data set, we interpret the data with a wide range of accompanying parameters that characterize the prevailing biogeochemical conditions and phytoplankton community physiology, activity, taxonomic composition, and capacity to cope with light stress. No correlations were observed with typical biomarker pigments for DMSP‐producing species. However, strong correlations were found between DMSP and primary production by cells >2 mm in diameter and between DMSP and some photo‐ protective pigments. These parameters are measures of mixed phytoplankton communities, so we infer that such associations are likely to be stronger in DMSP‐producing organisms. Further work is warranted to develop links between community parameters, DMS, and DMSP at the global scale. Citation: Bell, T. G., A. J. Poulton, and G. Malin (2010), Strong linkages between dimethylsulphoniopropionate (DMSP) and phytoplankton community physiology in a large subtropical and tropical Atlantic Ocean data set, Global Biogeochem. Cycles, 24, GB3009, doi:10.1029/2009GB003617.
Dimethyl sulfide (DMS) plays a major role in the global sulfur cycle. In addition, its atmospheric oxidation products contribute to the formation and growth of atmospheric aerosol particles, thereby influencing cloud condensation nuclei (CCN) populations and thus cloud formation. The pristine summertime Arctic atmosphere is a CCN-limited regime, and is thus very susceptible to the influence of DMS. However, atmospheric DMS mixing ratios have only rarely been measured in the summertime Arctic. During July–August 2014, we conducted the first high time resolution (10 Hz) DMS mixing ratio measurements for the Eastern Canadian Archipelago and Baffin Bay as one component of the Network on Climate and Aerosols: Addressing Key Uncertainties in Remote Canadian Environments (NETCARE). DMS mixing ratios ranged from below the detection limit of 4 to 1155 pptv (median 186 pptv). A set of transfer velocity parameterizations from the literature coupled with our atmospheric and coincident seawater DMS measurements yielded air-sea DMS flux estimates ranging from 0.02–12 μmol m−2 d−1, the first published for this region in summer. Airmass trajectory analysis using FLEXPART-WRF and chemical transport modeling using GEOS-Chem indicated that local sources (Lancaster Sound and Baffin Bay) were the dominant contributors to the DMS measured along the 21 day ship track, with episodic transport from the Hudson Bay System. After adjusting GEOS-Chem oceanic DMS values in the region to match measurements, GEOS-Chem reproduced the major features of the measured time series, but remained biased low overall (median 67 pptv). We investigated non-marine sources that might contribute to this bias, such as DMS emissions from lakes, biomass burning, melt ponds and coastal tundra. While the local marine sources of DMS dominated overall, our results suggest that non-local and possibly non-marine sources episodically contributed strongly to the observed summertime Arctic DMS mixing ratios.
Surface ocean biogeochemistry and photochemistry regulate ocean-atmosphere fluxes of trace gases critical for Earth's atmospheric chemistry and climate. The oceanic processes governing these fluxes are often sensitive to the changes in ocean pH (or pCO2) accompanying ocean acidification (OA), with potential for future climate feedbacks. Here, we review current understanding (from observational, experimental and model studies) on the impact of OA on marine sources of key climate-active trace gases, including dimethyl sulfide (DMS), nitrous oxide (N2O), ammonia and halocarbons. We focus on DMS, for which available information is considerably greater than for other trace gases. We highlight OA-sensitive regions such as polar oceans and upwelling systems, and discuss the combined effect of multiple climate stressors (ocean warming and deoxygenation) on trace gas fluxes. To unravel the biological mechanisms responsible for trace gas production, and to detect adaptation, we propose combining process rate measurements of trace gases with longer term experiments using both model organisms in the laboratory and natural planktonic communities in the field. Future ocean observations of trace gases should be routinely accompanied by measurements of two components of the carbonate system to improve our understanding of how in situ carbonate chemistry influences trace gas production. Together, this will lead to improvements in current process model capabilities and more reliable predictions of future global marine trace gas fluxes.
Arctic sea ice is retreating and thinning and its rate of decline has steepened in the last decades. While phytoplankton blooms are known to seasonally propagate along the ice edge as it recedes from spring to summer, the substitution of thick multiyear ice (MYI) with thinner, ponded first-year ice (FYI) represents an unequal exchange when considering the roles sea ice plays in the ecology and climate of the Arctic. Consequences of this shifting sea ice on the phenology of phytoplankton and the associated cycling of the climate-relevant gas dimethylsulfide (DMS) and its precursor dimethylsulfoniopropionate (DMSP) remain ill constrained. In July–August 2014, two contrasting ice edges in the Canadian High Arctic were explored: a FYI-dominated ice edge in Barrow Strait and a MYI-dominated ice edge in Nares Strait. Our results reveal two distinct planktonic systems and associated DMS dynamics in connection to these diverging ice types. The surface waters exiting the ponded FYI in Barrow Strait were characterized by moderate chlorophyll a (Chl a
We investigated distributions of surface water CO2 partial pressure (pCO2), dissolved oxygen (DO) and associated carbonate parameters in the Pearl River estuary, a large subtropical estuary under increasingly anthropogenic pressure in China, in the summer of 2000 and late spring of 2001. pCO2 levels, measured underway using a continuous measurement system, were high during both seasons, with levels of >4000 μatm at salinity <0.5. pCO2 distribution overall mirrored DO across the salinity gradient. Using the linear relationship between excess CO2 and apparent oxygen utilization (AOU) in surface water, we conclude that aerobic respiration is the most important process in maintaining such high pCO2 measured upstream. The material being respired is likely in a close association with the organic pollutants discharged into the system. Based on the measured excess CO2 vs. AOU plots, we estimate that the upper limit of pCO2 should be ∼7000 μatm in the Pearl River estuary assuming that CO2 was produced solely by aerobic respiration.
Due to anthropogenic activities, the nutrient loadings of the Changjiang (Yangtze River) are strickly on the rise. The high nutrient concentrations notwithstanding, river water was pCO2 supersaturated in the inner estuary during summer 2003 but decreased quickly in the mid-estuary due to mixing with low pCO2 waters from offshore. In addition, settling of particles in the estuary resulted in better light conditions so that phytoplankton bloomed, driving down pCO2 to ∼200 μatm. In the outer estuary and outside of the bloom area, pCO2 increased again to near or just below saturation. Literature data also reveal that the mainstream of the Changjiang is always supersaturated with respect to CO2 probably because the decomposition of terrestrial organic matter overwhelms the consumption of CO2 due to biological production.Because the Changjiang outflow accounts for 90% of the total river flow to the East China Sea (ECS), any variation in the Changjiang could have significant implications for the ECS. For instance, completion of the Three Gorge's Dam could change the metabolic status of the estuary by cutting off 70% of the downstream transport of organic carbon-containing particles. This would reduce the extent of organic carbon decomposition, producing better light conditions and enhancing autotrophy. As a result, the estuary could become a smaller source of CO2 to the atmosphere. On the other hand, if the Three Gorge's Dam reduced freshwater output, especially in summer, upwelling of nutrient-rich offshore waters would be reduced resulting in a reduction in autotrophy in the much wider ECS shelves. This effect could outweigh the reduced heterotrophy in the estuary and the ECS as a whole could become a smaller CO2 sink.
Dissolved inorganic carbon (DIC), total alkalinity (TAlk), pH, DO, and nutrients were measured in the Mississippi River plume during five cruises in spring, summer and fall. In contrast to other large rivers, both DIC and TAlk were higher in the river than in seawater and were removed along the mixing gradient between river and coastal water. In the intermediate salinity regions, the strong DIC removal was accompanied by strong nutrient removal, high dissolved oxygen (DO), high pH, and high chlorophyll a concentration. Net community production (NCP) rate estimated based on DIC and TAlk removal peaked during summer, and was among the highest observed for large river plumes. In summer and fall, 60-80% of the nutrient load from the Mississippi River was consumed in the plume, while only 30% of nutrient load was consumed in spring as the result of higher discharge, higher nutrient load, and lower productivity. Spatial and temporal changes in carbon and nutrient dynamics and NCP as well as a comparison with other large river plumes suggest that nutrient supply, light availability, temperature, and water residence time are the most important factors regulating NCP in this large river plume. Budget analysis suggests that the Mississippi River plume produces sufficient amount of labile organic carbon during March-June that meets the demand for developing the summer hypoxia of the northern Gulf of Mexico. CaCO3 precipitation is also likely, but the mechanism is still not clear.
Plastic is an allochthonous material to marine ecosystems but is rapidly colonized by marine microbial communities, with an as yet unclear contribution to biogeochemical cycles. In this study, we investigated the influence of an active microbial community grown on microplastic particles (the plastisphere) on CO2 and N2O recycling and its potential role in greenhouse gas inventories and air-sea exchange. Microplastics were collected during two cruises (Cimar 21 and FIP Montes Submarinos) from the surface layer (5 m depth) from several contrasting trophic regions of the South Pacific Ocean, i.e., from a transition zone off the eutrophic coastal upwelling of Chile, to a mesotrophic transition area of oceanic seamounts and, finally, to an oligotrophic zone in the South Pacific Subtropical Gyre. . Experiments were carried out onboard to evaluate CO2 and N2O production/consumption by the plastisphere. The active microbial community and its specific quantification were determined for Cimar 21 using iTag 16 S rRNA. The experiments showed that the plastisphere generally contributed to CO2 and N2O production/consumption, with rates ranging from -20.5 (consumption) to +4.5 (production) μmol/m2/d. The seamounts and the transition zone presented the highest production/consumption rates. The experiments performed in the two seamount stations showed that production and consumption of CO2 were related to the environmental nutrient concentration. Both stations presented N2O consumption that was associated with the high nitrogen deficit of the subantarctic water mass. The transition zone presented CO2 and N2O production in a plastisphere dominated by heterotrophic communities. The plastisphere in oligotrophic waters was diverse and active. The experiments, however, presented low or no production of greenhouse gases. Our results show a contribution of CO2 and N2O to the global gas surface inventories and air-sea exchange is lower than 1% of the global sources. These results highlight different critical impacts of plastic pollution on the environment that have, until now, not been considered.
The Eastern South Pacific coastal zone is characterized by seasonal and interannual variability, driven by upwelling and El Niño Southern Oscillation (ENSO), respectively. These oceanographical conditions influence microbial communities and their contribution to nutrient and greenhouse gases recycling, especially in bottom waters due to oxygenation. This article addresses the seasonal hydrographic and biogeochemical conditions in the water and sediments during El Niño 2015. Bottom water active microbial communities, including nitrifiers, were studied using amplicon sequencing of 16S rRNA (cDNA) and RT-qPCR, respectively. The results of the hydrographic analysis showed changes in the water column associated with the predominance of sub-Antarctic Waters characterized by warmed and low nutrients in the surface and more oxygenated conditions at the bottom in comparison with El Niño 2014. The organic matter quantity and quality decreased during fall and winter. The bottom water active microbial assemblages were dominated by archaea (Ca. Poseidoniales) and putative ammonia oxidizing archaea. Active bacteria affiliated to SAR11, Marinimicrobia and Nitrospina, and oxygen deficient realms (Desulfobacterales, SUP05 clade and anammox) suffered variations, possibly associated with oxygen and redox conditions in the benthic boundary layer. Nitrifying functional groups contributed significantly more during late fall and winter which was consistent with higher bottom water oxygenation. Relationships between apparent oxygen utilization nitrate and nitrous oxide in the water support the contribution of nitrification to this greenhouse gas distribution in the water. In general, our study suggests that seasonal oceanographic variability during an El Niño year influences the microbial community and thus remineralization potential, which supports the need to carry out longer time series to identify the relevance of seasonality under ENSO in Eastern Boundary Upwelling Systems (EBUS) areas.
Data presented in this paper are part of an extensive investigation of the physics of cross-shelf water mass exchange in the northeast of New Zealand and its effect on biological processes. Levels of dissolved dimethylsulfide (DMS) were quantified in relation to physical processes and phytoplankton biomass. Measurements were made at three main sites over the northeast continental shelf of New Zealand's North Island during a current-driven upwelling event in late spring 1996 (October) and an oceanic surface water intrusion event in summer 1997 (January). DMS concentrations in the euphotic zone ranged between 0.4 and 12.9 nmol dm 3. Integrated water column DMS concentrations ranged from 33 to 173 mmol m 2 in late spring during the higher biomass (15–62 Chl-a mg m 2) month of October, and from 25 to 38 mmol m 2 in summer during the generally lower biomass (16–42 Chl-a mg m 2) month of January. We observed high levels of DMS in the surface waters at an Inner Shelf site in association with a Noctiluca scintillans bloom which is likely to have enhanced lysis of DMSP-producing algal cells during phagotrophy. Integrated DMS concentrations increased threefold at a Mid Shelf site over a period of a week in conjunction with a doubling of algal biomass. A high correlation (r 2 0.911, significant 0.001) of integrated DMS and chlorophyll-a concentrations for compiled data from all stations indicated that chlorophyll-a biomass may be a reasonable predictor of DMS in this region, even under highly variable hydrographic conditions. Integrated bacterial production was inversely correlated to DMS production, indicating active bacterial consumption of DMS and/or its precursor.
Changes in iron supply to oceanic plankton are thought to have a significant effect on concentrations of atmospheric carbon dioxide by altering rates of carbon sequestration, a theory known as the 'iron hypothesis'. For this reason, it is important to understand the response of pelagic biota to increased iron supply. Here we report the results of a mesoscale iron fertilization experiment in the polar Southern Ocean, where the potential to sequester iron-elevated algal carbon is probably greatest. Increased iron supply led to elevated phytoplankton biomass and rates of photosynthesis in surface waters, causing a large drawdown of carbon dioxide and macronutrients, and elevated dimethyl sulphide levels after 13 days. This drawdown was mostly due to the proliferation of diatom stocks. But downward export of biogenic carbon was not increased. Moreover, satellite observations of this massive bloom 30 days later, suggest that a sufficient proportion of the added iron was retained in surface waters. Our findings demonstrate that iron supply controls phytoplankton growth and community composition during summer in these polar Southern Ocean waters, but the fate of algal carbon remains unknown and depends on the interplay between the processes controlling export, remineralisation and timescales of water mass subduction.
The impact of in situ iron fertilisation on the production of particulate dimethylsulphoniopropionate (DMSPp) and its breakdown product dimethyl sulphide (DMS) was monitored during the SOLAS air–sea gas exchange experiment (SAGE). The experiment was conducted in the high nitrate, low chlorophyll (HNLC) waters of the sub-Antarctic Southern Ocean (46.7°S 172.5°E) to the south-east of New Zealand, during March–April, 2004. In addition to monitoring net changes in the standing stocks of DMSPp and DMS, a series of dilution experiments were used to determine the DMSPp production and consumption rates in relation to increased iron availability. In contrast to previous experiments in the Southern Ocean, DMS concentrations decreased over the course of the 15-d iron-fertilisation experiment, from an integrated volume-specific concentration in the mixed layer on day 0 of 0.78nM (measured values 0.65–0.91nM) to 0.46nM (measured values 0.42–0.47nM) by day 15, in parallel with the surrounding waters. DMSPp, chlorophyll a and the abundance of photosynthetic picoeukaryotes exhibited indiscernible or only moderate increases in response to the raised iron availability, despite an obvious physiological response by the phytoplankton. High specific growth rates of DMSPp, equivalent to 0.8–1.2doublings d−1, occurred at the simulated 60% light level of the dilution experiments. Despite the high production rates, DMSPp accumulation was suppressed in part by microzooplankton grazers who consumed between 61%d−1 and 126%d−1 of the DMSPp production. Temporal trends in the rates of production and consumption illustrated a close coupling between the DMSP-producing phytoplankton and their microzooplankton grazers. Similar grazing and production rates were observed for the eukaryotic picophytoplankton that dominated the phytoplankton biomass, partial evidence that picoeukaryotes contributed a substantial proportion of the DMSP synthesis. These rates for DMSPp and picoeukaryotes were considerably higher than for chlorophyll a, indicating higher cycling rates of the DMSP-producing taxa than for the bulk phytoplankton community. When compared to the total phytoplankton community, there was no evidence of selection against the DMSP-containing phytoplankton by the microzooplankton grazers; the opposite appeared to be the case. SAGE demonstrated that increased iron availability in the HNLC waters of the Southern Ocean does not invariably lead to enhanced DMS sea–air flux. The potential suppression of DMSPp accumulation by grazers needs to be taken into account in future attempts to elevate DMS emission through in situ iron fertilisation and in understanding the hypothesised link between levels of Aeolian iron deposition in the Southern Ocean, DMS emission and global albedo.
As ocean acidification (OA) sensor technology develops and improves, in situ deployment of such sensors is becoming more widespread. However, the scientific value of these data depends on the development and application of best practices for calibration, validation, and quality assurance as well as on further development and optimization of the measurement technologies themselves. Here, we summarize the results of a 2-day workshop on OA sensor best practices held in February 2018, in Victoria, British Columbia, Canada, drawing on the collective experience and perspectives of the participants. The workshop on in situ Sensors for OA Research was organized around three basic questions: 1) What are the factors limiting the precision, accuracy and reliability of sensor data? 2) What can we do to facilitate the quality assurance/quality control (QA/QC) process and optimize the utility of these data? and 3) What sort of data or metadata are needed for these data to be most useful to future users? A synthesis of the discussion of these questions among workshop participants and conclusions drawn is presented in this paper.
Atmospheric iron and underway sea-surface dissolved (<0.2 μm) iron (DFe) concentrations were investigated along a north–south transect in the eastern Atlantic Ocean (27°N/16°W–19°S/5°E). Fe concentrations in aerosols and dry deposition fluxes of soluble Fe were at least two orders of magnitude higher in the Saharan dust plume than at the equator or at the extreme south of the transect. A weaker source of atmospheric Fe was also observed in the South Atlantic, possibly originating in southern Africa via the north-easterly outflow of the Angolan plume. Estimations of total atmospheric deposition fluxes (dry plus wet) of soluble Fe suggested that wet deposition dominated in the intertropical convergence zone, due to the very high amount of precipitation and to the fact that a substantial part of Fe was delivered in dissolved form. On the other hand, dry deposition dominated in the other regions of the transect (73–97%), where rainfall rates were much lower. Underway sea-surface DFe concentrations ranged 0.02–1.1 nM. Such low values (0.02 nM) are reported for the first time in the Atlantic Ocean and may be (co)-limiting for primary production. A significant correlation (Spearman's rho=0.862, p<0.01) was observed between mean DFe concentrations and total atmospheric deposition fluxes, confirming the importance of atmospheric deposition on the iron cycle in the Atlantic. Residence time of DFe in the surface waters relative to atmospheric inputs were estimated in the northern part of our study area (17±8 to 28±16 d). These values confirmed the rapid removal of Fe from the surface waters, possibly by colloidal aggregation.
Author Posting. © American Geophysical Union, 2005. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 19 (2005): GB4006, doi:10.1029/2004GB002445. We report iron measurements for water column and aerosol samples collected in the Sargasso Sea during July-August 2003 (summer 2003) and April-May 2004 (spring 2004). Our data reveal a large seasonal change in the dissolved iron (dFe) concentration of surface waters in the Bermuda Atlantic Time-series Study region, from ∼1–2 nM in summer 2003, when aerosol iron concentrations were high (mean 10 nmol m−3), to ∼0.1–0.2 nM in spring 2004, when aerosol iron concentrations were low (mean 0.64 nmol m−3). During summer 2003, we observed an increase of ∼0.6 nM in surface water dFe concentrations over 13 days, presumably due to eolian iron input; an estimate of total iron deposition over this same period suggests an effective solubility of 3–30% for aerosol iron. Our summer 2003 water column profiles show potentially growth-limiting dFe concentrations (0.02–0.19 nM) coinciding with a deep chlorophyll maximum at 100–150 m depth, where phytoplankton biomass is typically dominated by Prochlorococcus during late summer. Funding for this work was provided by the U.S. National Science Foundation (OCE-0222053 to P. N. S., OCE-0222046 to T. M. C., and OCE-0241310 to D. J. M.), the U.S. National Aeronautics and Space Administration (NAG5-11265 to D. J. M.), the Australian Research Council (DP0342826 to A. R. B.), the Antarctic Climate and Ecosystems Cooperative Research Center, and the H. Unger Vetlesen Foundation.
We present a dataset of dissolved methane (CH4) in the East China Sea (ECS) during five cruises in March, May, August, October and December 2011. CH4 distribution in this region showed pronounced spatial and seasonal variability due to the complex mixing of different water masses and other variables. Surface CH4 concentrations gradually decreased from the coast to the open sea, with maximum values occurring near Changjiang estuary or outside the Hangzhou Bay. The annual mean CH4 concentration of the surface layer was 9.1 ± 1.6 nmol L⁻¹ in the coastal area, which was nearly twice as large as that in the open sea (4.3 ± 1.3 nmol L⁻¹). CH4 was distributed evenly from the surface to the bottom in the shelf region during March and December, while it increased gradually with depth during May and October. CH4 depth profiles exhibited various distribution features along the coast, in the middle and on the edge of continental shelf. CH4 levels at the bottom were generally higher than at the surface during all seasons, indicating obvious CH4 sources from sediments. Incubation experiments of sediment cores onboard suggested that sediment release was an important source of CH4 in the water column of the ECS. We estimated that the annual average CH4 release rate from sediments was about 1.11 μmol·m⁻²·d⁻¹ on the continental shelf of the ECS. The maximum CH4 concentration and sediment-water CH4 flux both occurred in summer, which might be related with the occurrence of hypoxia in the bottom water. Surface seawater of the ECS was oversaturated with CH4 relative to the atmosphere over most of the five cruises, indicating that the ECS was a net source of atmospheric CH4. The annual mean area-weighted sea-air flux density of CH4 in the ECS was estimated to be about 10.7 μmol·m⁻²·d⁻¹ in 2011. Accordingly, an area-weighted, seasonally adjusted annual rate of CH4 efflux was determined to be 2.98 × 10⁹ mol yr⁻¹ (∼0.05 Tg CH4 yr⁻¹) from the ECS to the atmosphere.
Distributions and fluxes of methane were determined during two surveys in March-May 2001 in the Yellow Sea and the East China Sea. Methane concentrations in the surface and bottom waters range from 2.52 to 5.48 and 2.81 to 8.17 nM, respectively. The distributions of methane are influenced obviously by the Yangtze River effluent and Kuroshio water. CH4 input via the Yangtze River is estimated to be 3.17 mol/s, of which a considerable part may be lost by air-sea exchange during estuarine mixing. Net CH4 flux exported from the shelf to the Kuroshio is about 1.84 mol/s. Methane enrichments in bottom waters occur widely, which reveals sediment sources of CH4. However, the CH4 input from the sediments of the studied region in spring is lower than other shelf regions due to low organic carbon in the sediments and high O2 contents in the water column. The sea-to-air methane fluxes are estimated to be 1.36 +/- 1.45 and 2.30 +/- 2.36 mumol m-2 d-1 using Liss and Merlivat  and Wanninkhof  relationships, respectively, and the estimated spring emission rate of methane ranges from 9.32 × 10-3 to 15.7 × 10-3 Tg CH4 yr-1. However, these estimations suffer from the neglect of seasonal variability and should be taken as a low limit. Therefore more measurement campaigns should be carried out to enhance our understanding of this particular oceanic region.