Posts Tagged 'chemistry'



Contrasting land-uses in two small river basins impact the colored dissolved organic matter concentration and carbonate system along a river-coastal ocean continuum

Highlights

  • Contrasting land use in basins influences CDOM proportions in river-coastal continuum.
  • CDOM/fDOM proportions fluvial may influence the carbonate system of coastal.
  • River with high CDOM proportions have implications for mussel farming.
  • High CDOM/fDOM proportion be associated with corrosive conditions in river waters.

Abstract

Human activities have led to an increase in land use change, with effects on the structure and functioning of ecosystems. The impact of contrasting land uses along river basins on the concentration of colored dissolved organic matter (CDOM) reaching the coastal zone, and its relationship with the carbonate system of the adjacent coastal ocean, is poorly known. To understand the relationship between land use change, CDOM and its influence on the carbonate system, two watersheds with contrasting land uses in southern Chile were studied. The samples were collected at eight stations between river and adjacent coastal areas, during three sampling campaigns in the austral summer and spring. Chemical and biological samples were laboratory analysis according to protocols. Landsat 8 satellite images of the study area were used for identification and supervised classification using remote sensing tools. The Yaldad River basin with 82% of native forest and the Colu River basin with 38% of grassland (agriculture). Low total alkalinity (AT) and Dissolved Inorganic Carbon (DIC), but high CDOM proportions were observed in freshwater. A higher CDOM and humic-like compounds concentration was observed along the river-coastal ocean continuum in the Yaldad basin, characterized by a predominance of native forests. In contrast, nutrient concentrations, AT and DIC, were higher in the Colu area. Low CaCO3 saturation state (ΩAr < 2) and even undersaturation conditions were observed at the coastal ocean at Yaldad. A strong negative correlation between AT, DIC and ΩAr with CDOM/fDOM, suggested the influence of terrestrial material on the seawater carbon chemistry. Our results provide robust evidence that land uses in river basins can influence CDOM/fDOM proportion and its influence on the carbonate chemistry of the adjacent coastal, with potential implications for the shellfish farming activity in this region.

Continue reading ‘Contrasting land-uses in two small river basins impact the colored dissolved organic matter concentration and carbonate system along a river-coastal ocean continuum’

Modeling of biogeochemical consequences of a CO2 leak in the water column with bottom anoxia

Highlights

  • To study the biogeochemical consequences of a release of CO2 in an anoxic marine environment a FABM family set of models consisting of a transport model, biogeochemical model (including carbonate system processes block) and bubble fate (transport and dissolution) was applied.
  • The measurements performed during a controlled 2-h long CO2 release experiments show elevated levels of pCO2 and simultaneously decreased values in pH, that was used for the model validation.
  • The model analysis of consequences of a CO2discharge demonstrates that CO2 bubbles are dissolved shortly after termination of the leak, while changes in pH, pCO2 and TIC can be detected for several days after the leak, but only at a limited distance from the source (< 10 m in the examples evaluated here).

Abstract

In this paper we investigate the spatial extent and biogeochemical properties of a known CO2 plume using the pelagic transport-biogeochemical model BROM (Bottom RedOx Model). The model consists of a biogeochemical module, a 2-dimensional vertical transport module and gas bubble fate module, parameterizing bubbles rising and dissolution according to existing approaches. A controlled CO2 release experiment was carried out in the Horten Inner Harbor, Norway, in September 2018. This isolated bay is characterized by limited water mixing and anoxia in the bottom layer. CO2 was released at a water depth of 18 m either in a gas phase or dissolved in seawater at leak rates ranging from 0.1 l/min to 15.8 l/min. The chemical response to the release events relative to background variations was measured using chemical sensors mounted on two seabed templates located 4 m and 15 m from the release point, respectively, and compared to the values predicted by the model. The measurements show elevated levels of pCO2 and simultaneously decreased values in pH corresponding to the controlled release experiments. The model’s simulations were in good agreement with the baseline observations and the measured changes forced by the experimental leak. The model predicts that after a continuous leak of this magnitude in stagnant conditions of anoxic bottom water, a 2–3 weeks long restoration period occurs, after which the disturbances disappear. This work confirms that the footprint of a potential CO2 leak is localized in the vicinity of the source (tens of meters) where it can be detectable with available chemical sensors.

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Dissolution of a submarine carbonate platform by a submerged lake of acidic seawater

Submarine sinkholes are found on carbonate platforms around the world. They are thought to form and grow when groundwater interactions generate conditions corrosive to carbonate minerals. Because their morphology can restrict mixing and water exchange, the effects of biogeochemical processes can accumulate such that the sinkhole water properties considerably diverge from the surrounding ocean. Studies of sinkhole waters can therefore reveal new insights into marine biogeochemical cycles, thus sinkholes can be considered as ‘natural laboratories’ where the response of marine ecosystems to environmental variations can be investigated. We conducted the first measurements in recently discovered sinkholes on Luymes Bank, part of Saba Bank in the Caribbean Netherlands. Our measurements revealed a plume of gas bubbles rising from the seafloor in one of the sinkholes, which contained a constrained body of dense, low-oxygen ([O2] = 60.2 ± 2.6 μmol · kg−1), acidic (pHT = 6.24 ± 0.01) seawater that we term the ‘acid lake’. Here, we investigate the physical and biogeochemical processes that gave rise to and sustain the acid lake, the chemistry of which is dominated by the bubble plume. We determine the provenance and fate of the acid lake’s waters, which we deduce must be continuously flowing through. We show that the acid lake is actively dissolving the carbonate platform, so the bubble plume may provide a novel mechanism for submarine sinkhole formation and growth. It is likely that the bubble plume is ephemeral and that other currently non-acidic sinkholes on Luymes Bank have previously experienced ‘acid lake’ phases. Conditions within the acid lake are too extreme to represent coming environmental change on human timescales but in some respects reflect the bulk ocean billions of years ago. Other Luymes Bank sinkholes host conditions analogous to projections for the end of the 21st century and could provide a venue for studies on the impacts of anthropogenic CO2 uptake by the ocean.

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Benthic organic matter transformation drives pH and carbonate chemistry in Arctic marine sediments

The carbonate chemistry of Arctic Ocean seafloor and its vulnerability to ocean acidification remains poorly explored. This limits our ability to quantify how biogeochemical processes and bottom water conditions shape sedimentary carbonate chemistry, and to predict how climate change may affect such biogeochemical processes at the Arctic Ocean seafloor. Here, we employ an integrated model assessment that explicitly resolves benthic pH and carbonate chemistry along a S—N transect in the Barents Sea. We identify the main drivers of observed carbonate dynamics and estimate benthic fluxes of dissolved inorganic carbon and alkalinity to the Arctic Ocean. We explore how bottom water conditions and in-situ organic matter degradation shape these processes and show that organic matter transformation strongly impacts pH and carbonate saturation (Ω) variations. Aerobic organic matter degradation drives a negative pH shift (pH &lt; 7.6) in the upper 2—5 cm, producing Ω &lt; 1. This causes shallow carbonate dissolution, buffering porewater pH to around 8.0. Organic matter degradation via metal oxide (Mn/Fe) reduction pathways further increases pH and carbonate saturation state. At the northern stations, where Ω &gt; 5 at around 10–25 cm, model simulations result in authigenic carbonate precipitation. Furthermore, benthic fluxes of dissolved inorganic carbon (12.5—59.5 &micro;mol cm−2 yr−1) and alkalinity (11.3—63.2 &micro;mol cm−2 yr−1) are 2—3-fold greater in the northern sites due to greater carbonate dissolution. Our assessment is of significant relevance to predict how changes in the Arctic Ocean may shift carbon burial and pH buffering into the next century.

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The Bouraké semi-enclosed lagoon (New Caledonia) – a natural laboratory to study the lifelong adaptation of a coral reef ecosystem to extreme environmental conditions (update)

According to current experimental evidence, coral reefs could disappear within the century if CO2 emissions remain unabated. However, recent discoveries of diverse and high cover reefs that already live under extreme conditions suggest that some corals might thrive well under hot, high-pCO2, and deoxygenated seawater. Volcanic CO2 vents, semi-enclosed lagoons, and mangrove estuaries are unique study sites where one or more ecologically relevant parameters for life in the oceans are close to or even worse than currently projected for the year 2100. Although they do not perfectly mimic future conditions, these natural laboratories offer unique opportunities to explore the mechanisms that reef species could use to keep pace with climate change. To achieve this, it is essential to characterize their environment as a whole and accurately consider all possible environmental factors that may differ from what is expected in the future, possibly altering the ecosystem response.

This study focuses on the semi-enclosed lagoon of Bouraké (New Caledonia, southwest Pacific Ocean) where a healthy reef ecosystem thrives in warm, acidified, and deoxygenated water. We used a multi-scale approach to characterize the main physical-chemical parameters and mapped the benthic community composition (i.e., corals, sponges, and macroalgae). The data revealed that most physical and chemical parameters are regulated by the tide, strongly fluctuate three to four times a day, and are entirely predictable. The seawater pH and dissolved oxygen decrease during falling tide and reach extreme low values at low tide (7.2 pHT and 1.9 mg O2 L−1 at Bouraké vs. 7.9 pHT and 5.5 mg O2 L−1 at reference reefs). Dissolved oxygen, temperature, and pH fluctuate according to the tide by up to 4.91 mg O2 L−1, 6.50 C, and 0.69 pHT units on a single day. Furthermore, the concentration of most of the chemical parameters was 1 to 5 times higher at the Bouraké lagoon, particularly for organic and inorganic carbon and nitrogen but also for some nutrients, notably silicates. Surprisingly, despite extreme environmental conditions and altered seawater chemical composition measured at Bouraké, our results reveal a diverse and high cover community of macroalgae, sponges, and corals accounting for 28, 11, and 66 species, respectively. Both environmental variability and nutrient imbalance might contribute to their survival under such extreme environmental conditions. We describe the natural dynamics of the Bouraké ecosystem and its relevance as a natural laboratory to investigate the benthic organism’s adaptive responses to multiple extreme environmental conditions.

Continue reading ‘The Bouraké semi-enclosed lagoon (New Caledonia) – a natural laboratory to study the lifelong adaptation of a coral reef ecosystem to extreme environmental conditions (update)’

Supply-controlled calcium carbonate dissolution decouples the seasonal dissolved oxygen and pH minima in Chesapeake Bay

Acidification can present a stress on organisms and habitats in estuaries in addition to hypoxia. Although oxygen and pH decreases are generally coupled due to aerobic respiration, pH dynamics may be more complex given the multiple modes of buffering in the carbonate system. We studied the seasonal cycle of dissolved oxygen (DO), pH, dissolved inorganic carbon, total alkalinity, and calcium ion (Ca2+) along the main channel of Chesapeake Bay from May to October in 2016. Contrary to the expected co-occurrence of seasonal DO and pH declines in subsurface water, we found that the pH decline ended in June while the DO decline continued until August in mid-Chesapeake Bay. We discovered that aerobic respiration was strong from May to August, but carbonate dissolution was minor in May and June and became substantial in August, which buffered further pH declines and caused the seasonal DO and pH minima mismatch. The rate of calcium carbonate (CaCO3) dissolution was not primarily controlled by the saturation state in bottom water, but was instead likely controlled by the supply of CaCO3 particles. The seasonal variability of Ca2+ addition in the mid-bay was connected to Ca2+ removal in the upper bay, and the timing of high carbonate dissolution coincided with peak seasonal biomass of upper Bay submerged aquatic vegetation. This study suggests a mechanism for a novel decoupling of DO and pH in estuarine waters associated with CaCO3, but future studies are needed to fully investigate the seasonality of physical transport and cycling of CaCO3.

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Seasonal cycle of surface ocean pCO2 and pH in the northern Indian Ocean and their controlling factors

Highlights

  • The maxima of seasonal amplitudes of pCO2 and pH occur during April-May and August-September for both the basins.
  • The western Arabian Sea has the largest seasonal variance of pCO2.
  • The contribution of ALK and S is complementary with each other in inducing seasonal variances of pCO2 and pH in the southeastern Arabian Sea.
  • This study highlights the hotspots of pCO2 and pH in the northern Indian Ocean, where observational efforts to monitor pCO2 and pH become an essential requirement.

Abstract

This paper examines the seasonal variability of surface ocean pCO2 and pH in the northern Indian Ocean. It aims to identify their controlling factors using a high-resolution, regional ocean-ecosystem model simulation and available surface ocean carbon observations. The seasonal variability of pCO2 and pH of the northern Indian Ocean is attributed to the changes in surface temperature (T), dissolved inorganic carbon (DIC), total alkalinity (ALK), and salinity (S). The western Arabian Sea has an enormous seasonal variance of pCO2 due to coastal upwelling dynamics. In contrast, the seasonal variance of pCO2 in the Bay of Bengal is governed by the upper ocean mixed layer dynamics, albeit with smaller amplitudes. The contribution of T (DIC) in the seasonal variance of pCO2 and pH at the western Arabian Sea is ±90 (∓100) μatm and ±0.18 (∓0.20) pH units, respectively. The contribution of ALK and S is complementary to each other in inducing seasonal variances of pCO2 and pH in the southeastern Arabian Sea with a magnitude of ±5∼10 μatm and ±0.02 pH units, respectively. In the northern Bay of Bengal, salinity plays a significant role in controlling seasonal variability of pCO2 and pH with amplitudes of roughly ± 20 µatm and ±0.18 pH units, respectively, along the pathways of freshwater spreading. The maxima of seasonal amplitudes of pCO2 and pH occur during April-May and August-September for both basins. This study highlights the hotspots of pCO2 and pH in the northern Indian Ocean, where observational efforts to monitor pCO2 and pH become an essential requirement.

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Impact of dust addition on Mediterranean plankton communities under present and future conditions of pH and temperature: an experimental overview (update)

In low-nutrient low-chlorophyll areas, such as the Mediterranean Sea, atmospheric fluxes represent a considerable external source of nutrients likely supporting primary production, especially during periods of stratification. These areas are expected to expand in the future due to lower nutrient supply from sub-surface waters caused by climate-driven enhanced stratification, likely further increasing the role of atmospheric deposition as a source of new nutrients to surface waters. Whether plankton communities will react differently to dust deposition in a warmer and acidified environment remains; however, an open question. The potential impact of dust deposition both in present and future climate conditions was investigated in three perturbation experiments in the open Mediterranean Sea. Climate reactors (300 L) were filled with surface water collected in the Tyrrhenian Sea, Ionian Sea and in the Algerian basin during a cruise conducted in the frame of the PEACETIME project in May–June 2017. The experiments comprised two unmodified control tanks, two tanks enriched with a Saharan dust analogue and two tanks enriched with the dust analogue and maintained under warmer (+3 C) and acidified (−0.3 pH unit) conditions. Samples for the analysis of an extensive number of biogeochemical parameters and processes were taken over the duration (3–4 d) of the experiments. Dust addition led to a rapid release of nitrate and phosphate, however, nitrate inputs were much higher than phosphate. Our results showed that the impacts of Saharan dust deposition in three different basins of the open northwestern Mediterranean Sea are at least as strong as those observed previously, all performed in coastal waters. The effects of dust deposition on biological stocks were different for the three investigated stations and could not be attributed to differences in their degree of oligotrophy but rather to the initial metabolic state of the community. Ocean acidification and warming did not drastically modify the composition of the autotrophic assemblage, with all groups positively impacted by warming and acidification. Although autotrophic biomass was more positively impacted than heterotrophic biomass under future environmental conditions, a stronger impact of warming and acidification on mineralization processes suggests a decreased capacity of Mediterranean surface plankton communities to sequester atmospheric CO2 following the deposition of atmospheric particles.

Continue reading ‘Impact of dust addition on Mediterranean plankton communities under present and future conditions of pH and temperature: an experimental overview (update)’

Role of river discharge and warming on ocean acidification and pCO2 levels in the Bay of Bengal

Shifts in surface ocean pCO2 and pH are important controls governing global climate. Based on the linear relationship of observed surface pH and pCO2 with sea surface temperature (SST), sea surface salinity (SSS) and Chlorophyll-a (Chl-a) multiple linear regression equations were developed. Based on remote sensing SST, Chl-a and model-derived SSS, pH and pCO2 data were derived from 1998 to 2015. Overall warming of BoB is noticed at the rate of 0.004° to 0.03 °C/y whereas cooling is found in the northwestern BoB during winter and spring seasons associated with an increase in atmospheric dust. Decrease in SSS is noticed during all seasons due to melting of Himalayan ice cover associated with increase in fresh water flux due to increase in atmospheric temperature. Increase in pH is observed in the eastern and southern Bay during all seasons associating with warming and decrease in salinity. In contrast, decrease in pH (−0.001 y−1) and pCO2 increase (+0.1 to +0.7 µatm y−1) is noticed in the western and head Bay during winter and spring seasons due to deposition of atmospheric pollutants. This study suggests that increase in freshwater input due to melting of Himalayan ice cover and deposition of atmospheric pollutants are dominant controlling factors on surface ocean pH and pCO2 in the BoB between 1998 and 2015 and this region is acting as a stronger sink for the atmospheric CO2 in the present than that in the past two decades. The global coastal regions are significantly influenced by river discharge and atmospheric deposition of pollutants and they are not part of the global models leading to ill-reproduction of seasonal variability in pH and pCO2. Inclusion of these processes may improve prediction of pH and pCO2 in the regions heavily influenced by discharge/deposition from land and atmosphere.

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Causes of increased dissolved inorganic carbon in the subsurface layers in the western shelfbreak and high latitude basin in the Arctic Pacific Sector

The expansion of Dissolved Inorganic Carbon (DIC)-rich water carried by the Pacific inflow creates a DIC maximum layer and exerts important influences on ocean acidification in the subsurface Arctic Ocean. This study analyzed shifts in the DIC distribution of the subsurface Arctic Ocean during 1998–2015 through hindcast simulation using a three-dimensional ocean-sea ice-biogeochemical model. For this purpose, the study was divided into two time periods (1998–2007 and 2008–2015). The results showed that the lower boundary layer of the Pacific Winter Water (PWW), defined as an isopycnal of 27 kg/m3, became deeper by ~50 m in the central Canada Basin and expanded northward during 2008–2015 relative to 1998–2007. Accordingly, the subsurface DIC maximum layer deepened and expanded northwards into the Makarov Basin at high latitudes around 85°N. During 2008–2015, DIC concentrations, averaged over a 50–250 m water column, increased significantly in the Chukchi-East Siberian Shelfbreak and Makarov Basin. The DIC increase over the shelfbreak is mainly attributable to increased local biological degradation and the transportation of DIC-rich water from the Chukchi Shelf through Barrow Canyon. Estimates of the DIC budget indicated that advection controlled the increase in DIC content in the Makarov Basin during 2008–2015. This is attributed to the shift of the ocean circulation pattern, in which the ocean current along the Chukchi-East Siberian Slope to the Makarov Basin became stronger during 2008–2015, promoting the transport of DIC-rich Pacific Water into the Makarov Basin.

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Integrated assessment of ocean acidification risks to pteropods in the Northern high latitudes: regional comparison of exposure, sensitivity and adaptive capacity

Exposure to the impact of ocean acidification (OA) is increasing in high-latitudinal productive habitats. Pelagic calcifying snails (pteropods), a significant component of the diet of economically important fish, are found in high abundance in these regions. Pteropods have thin shells that readily dissolve at low aragonite saturation state (Ωar), making them susceptible to OA. Here, we conducted a first integrated risk assessment for pteropods in the Eastern Pacific subpolar gyre, the Gulf of Alaska (GoA), Bering Sea, and Amundsen Gulf. We determined the risk for pteropod populations by integrating measures of OA exposure, biological sensitivity, and resilience. Exposure was based on physical-chemical hydrographic observations and regional biogeochemical model outputs, delineating seasonal and decadal changes in carbonate chemistry conditions. Biological sensitivity was based on pteropod morphometrics and shell-building processes, including shell dissolution, density and thickness. Resilience and adaptive capacity were based on species diversity and spatial connectivity, derived from the particle tracking modeling. Extensive shell dissolution was found in the central and western part of the subpolar gyre, parts of the Bering Sea, and Amundsen Gulf. We identified two distinct morphotypes: L. helicina helicina and L. helicina pacifica, with high-spired and flatter shells, respectively. Despite the presence of different morphotypes, genetic analyses based on mitochondrial haplotypes identified a single species, without differentiation between the morphological forms, coinciding with evidence of widespread spatial connectivity. We found that shell morphometric characteristics depends on omega saturation state (Ωar); under Ωar decline, pteropods build flatter and thicker shells, which is indicative of a certain level of phenotypic plasticity. An integrated risk evaluation based on multiple approaches assumes a high risk for pteropod population persistence with intensification of OA in the high latitude eastern North Pacific because of their known vulnerability, along with limited evidence of species diversity despite their connectivity and our current lack of sufficient knowledge of their adaptive capacity. Such a comprehensive understanding would permit improved prediction of ecosystem change relevant to effective fisheries resource management, as well as a more robust foundation for monitoring ecosystem health and investigating OA impacts in high-latitudinal habitats.

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Integrating environmental variability to broaden the research on coral responses to future ocean conditions

Our understanding of the response of reef-building corals to changes in their physical environment is largely based on laboratory experiments, analysis of long-term field data, and model projections. Experimental data provide unique insights into how organisms respond to variation of environmental drivers. However, an assessment of how well experimental conditions cover the breadth of environmental conditions and variability where corals live successfully is missing. Here, we compiled and analyzed a globally distributed dataset of in-situ seasonal and diurnal variability of key environmental drivers (temperature, pCO2, and O2) critical for the growth and livelihood of reef-building corals. Using a meta-analysis approach, we compared the variability of environmental conditions assayed in coral experimental studies to current and projected conditions in their natural habitats. We found that annual temperature profiles projected for the end of the 21st century were characterized by distributional shifts in temperatures with warmer winters and longer warm periods in the summer, not just peak temperatures. Furthermore, short-term hourly fluctuations of temperature and pCO2 may regularly expose corals to conditions beyond the projected average increases for the end of the 21st century. Coral reef sites varied in the degree of coupling between temperature, pCO2, and dissolved O2, which warrants site-specific, differentiated experimental approaches depending on the local hydrography and influence of biological processes on the carbonate system and O2 availability. Our analysis highlights that a large portion of the natural environmental variability at short and long timescales is underexplored in experimental designs, which may provide a path to extend our understanding on the response of corals to global climate change.

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The role of algal blooms and community respiration in controlling the temporal and spatial dynamics of hypoxia and acidification in eutrophic estuaries

While hypoxia and acidification can be common occurrences in eutrophic coastal zones, the precise, coupled temporal and spatial dynamics of these conditions are poorly described. Here, continuous measurements of water column pH, pCO2, carbonate chemistry, and dissolved oxygen (DO) concentrations were made from spring through fall across two, temperate eutrophic estuaries, western Long Island Sound (LIS) and Jamaica Bay, NY, USA. Vertical dynamics were resolved using an underway towing profiler and an automated stationary profiling unit. During the study, high rates of respiration in surface and bottom waters (> -0.2 mg O2 L-1 h-1) yielded strongly negative rates of net ecosystem metabolism during the summer (-4 to -8 g O2 m-2 d-1). Ephemeral surface algal blooms caused brief periods (< one week) of basification and supersaturation of DO that were succeeded by longer periods of acidification and hypoxia. In deeper regions, hypoxia (< 2 mg L-1 DO) and acidic water (pH < 7; total scale; pCO2 levels >2000 μatm) that persisted continuously for >40 days in both estuaries was often overlain by water with higher DO and pH. Diurnal vertical profiles demonstrated that oxic surface waters saturated with respect to calcium carbonate and DO during the day transitioned to unsaturated and hypoxic at night. Evidence is presented that, beyond respiration, nitrification in surface water promoted by sewage discharge and oxidation processes in sediments also contribute to acidification in these estuaries. Collectively, this study demonstrates the pervasive, persistent, and dynamic nature of hypoxia and acidification in eutrophic estuaries are likely to shape marine food webs.

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Cyanobacteria net community production in the Baltic Sea as inferred from profiling pCO2 measurements

Organic matter production by cyanobacteria blooms is a major environmental concern for the Baltic Sea, as it promotes the spread of anoxic zones. Partial pressure of carbon dioxide (pCO2) measurements carried out on Ships of Opportunity (SOOP) since 2003 have proven to be a powerful tool to resolve the carbon dynamics of the blooms in space and time. However, SOOP measurements lack the possibility to directly constrain depth-integrated net community production (NCP) in moles of carbon per surface area due to their restriction to the sea surface. This study tackles the knowledge gap through (1) providing an NCP best guess for an individual cyanobacteria bloom based on repeated profiling measurements of pCO2 and (2) establishing an algorithm to accurately reconstruct depth-integrated NCP from surface pCO2 observations in combination with modelled temperature profiles.

Goal (1) was achieved by deploying state-of-the-art sensor technology from a small-scale sailing vessel. The low-cost and flexible platform enabled observations covering an entire bloom event that occurred in July–August 2018 in the Eastern Gotland Sea. For the biogeochemical interpretation, recorded pCO2 profiles were converted to C∗T, which is the dissolved inorganic carbon concentration normalised to alkalinity. We found that the investigated bloom event was dominated by Nodularia and had many biogeochemical characteristics in common with blooms in previous years. In particular, it lasted for about 3 weeks, caused a C∗T drawdown of 90 µmol kg−1, and was accompanied by a sea surface temperature increase of 10 C. The novel finding of this study is the vertical extension of the C∗T drawdown up to the compensation depth located at around 12 m. Integration of the C∗T drawdown across this depth and correction for vertical fluxes leads to an NCP best guess of ∼1.2 mol m−2 over the productive period.

Addressing goal (2), we combined modelled hydrographical profiles with surface pCO2 observations recorded by SOOP Finnmaid within the study area. Introducing the temperature penetration depth (TPD) as a new parameter to integrate SOOP observations across depth, we achieve an NCP reconstruction that agrees to the best guess within 10 %, which is considerably better than the reconstruction based on a classical mixed-layer depth constraint.

Applying the TPD approach to almost 2 decades of surface pCO2 observations available for the Baltic Sea bears the potential to provide new insights into the control and long-term trends of cyanobacteria NCP. This understanding is key for an effective design and monitoring of conservation measures aiming at a Good Environmental Status of the Baltic Sea.

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First record of straight-needle pteropod Creseis acicula Rang, 1828 bloom in the Çanakkale Strait (NE Aegean Sea, Turkey)

Pteropods are marine pelagic calcifier mollusks sensitive to chemical changes in seawater due to their highly soluble aragonite shells. Increased acidity (reduced pH) of seawater causes difficulties in precipitating their shells and/or results in their dissolution, which is related to increased atmospheric CO2 concentrations and warming of seawater. They are therefore indicators of environmental changes. In this paper, we present the first record of the straight-needle pteropod Creseis acicula Rang, 1828 bloom in the surface waters of the Ҫanakkale Strait, Turkey (NE Aegean Sea), encountered in July 2020, when the highest sea surface temperatures and pH levels since 2007 were recorded. In coastal zones, such as the Ҫanakkale Strait, anthropogenic activity contributes significantly to environmental changes. Consequently, the increase in pH at elevated temperatures indicates an auxiliary factor (i.e. anthropogenic activity) that triggered the C. acicula bloom, rather than global atmospheric CO2 levels.

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Hydrogeochemistry and acidic property of submarine groundwater discharge around two coral islands in the Northern South China Sea

Submarine groundwater discharge (SGD) is an important source of nutrients in many coastal regions, yet little information is available on its carbonate chemistry and controlling factors. This study examined the processes and factors controlling the hydrogeochemistry and acidic property of the groundwaters and SGD waters of two isolated coral islands, Liuqiu Island (13 km off southwestern Taiwan) and Dongsha Island (located in the northern South China Sea, 420 km away from Liuqiu Island). Our results showed that the total alkalinity and dissolved inorganic carbon (DIC) of the fresh SGD waters were controlled mainly by the chemical weathering of carbonate minerals. Part of the DIC came from the organic matter decomposition or soil CO2, reducing the pH and CO32− concentration. Distributions of the carbonate chemistry and nutrients of the SGD waters were controlled mainly by physical mixing between the groundwater and the ambient seawater under the seabed, the so-called subterranean estuary. The Ca2+ released through weathering significantly increased the saturation state of aragonite or calcite, reducing the corrosiveness of the SGD waters on the carbonate rocks. This study is likely the first to examine the effects of the acidic property of SGD waters on the biogenic carbonate spine of a sea urchin and a pteropod shell. The spring water with similar carbonate chemistry to that of the freshwater SGD endmember from Liuqiu Island with a saturation state of aragonite of 0.96 caused observable dissolution on the spine of a sea urchin and a pteropod shell, but the spine dissolved more readily. This was because the spine is made of high-Mg calcite, which has higher solubility than that of aragonite or calcite. Such a result implies that some marine organisms with carbonate skeletons or shells containing high Mg:Ca ratios may suffer the impact of ocean acidification earlier. Although the SGD may contribute less than 10% of freshwater discharge by rivers to the coastal area, its impact on coastal biogeochemical cycles and ecosystems due to its acidic property and continual effect on the coast all year round deserves further investigation.

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Reconstruction of global surface ocean pCO2 using region-specific predicators based on a stepwise FFNN regression algorithm

Various machine learning methods were attempted in the global mapping of surface ocean partial pressure of CO2 (pCO2) to reduce the uncertainty of global ocean CO2 sink estimate due to undersampling of pCO2. In previous researches the predicators of pCO2 were usually selected empirically based on theoretic drivers of surface ocean pCO2 and same combination of predictors were applied in all areas unless lack of coverage. However, the differences between the drivers of surface ocean pCO2 in different regions were not considered. In this work, we combined the stepwise regression algorithm and a Feed Forward Neural Network (FFNN) to selected predicators of pCO2 based on mean absolute error in each of the 11 biogeochemical provinces defined by Self-Organizing Map (SOM) method. Based on the predicators selected, a monthly global 1° × 1° surface ocean pCO2 product from January 1992 to August 2019 was constructed. Validation of different combination of predicators based on the SOCAT dataset version 2020 and independent observations from time series stations was carried out. The prediction of pCO2 based on region-specific predicators selected by the stepwise FFNN algorithm were more precise than that based on predicators from previous researches. Appling of a FFNN size improving algorithm in each province decreased the mean absolute error (MAE) of global estimate to 11.32 μatm and the root mean square error (RMSE) to 17.99 μatm. The script file of the stepwise FFNN algorithm and pCO2 product are distributed through the Institute of Oceanology of the Chinese Academy of Sciences Marine Science Data Center (IOCAS; http://dx.doi.org/10.12157/iocas.2021.0022, Zhong et al., 2021).

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Effect of pH and type of stirring on the spontaneous precipitation of CaCO3 at identical initial supersaturation, ionic strength and a(Ca2+)/a(CO32−) ratio

CaCO3 precipitation is physical-chemical basis of biomineral formation of hard tissue (shells, skeletons) in marine calcifying organisms (=biomineralization). Processes controlling biomineralization are still not fully clarified, so the study of influence of pH on basic processes of CaCO3 precipitation should contribute to better understanding of biomineralization under climate change. This paper reports on the effect of initial pH (pH0) and type of stirring (mechanical and magnetical) on spontaneous precipitation and phase composition, size and morphology of spontaneously precipitated CaCO3 formed at the identical initial supersaturation, ionic strength and a(Ca2+)/a(CO32−) ratio. The initial pH varied in a range 8.50 ≤ pH0 ≤ 10.50 and included values relevant for mimicking the conditions related to biomineralization in marine organisms. In all systems two CaCO3 polymorphs were found: calcite and/or vaterite. The increase of pH0 favoured the formation of rhombohedral calcite no matter the type of stirring. This was exclusively influenced by the systems’ pH0 (other relevant initial parameters were identical). Furthermore, increase of pH0 caused change of vaterite morphology from cauliflower-like spheroids to regular spherulites. The mechanically stirred systems produced larger calcite and vaterite particles and higher content of calcite.

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Acidification and deoxygenation of the Northwestern Japan/East Sea

Seasonal hypoxia in the bottom waters of the Peter the Great Bay (PGB) of the Japan/East Sea (JES) occurs in summer. Using the empirical relationship between dissolved oxygen (DO) and pH obtained for hypoxic conditions and available historical DO data, acidification rates were estimated. Carefully sampled time-series observations from the northwestern part of the JES, carried out from 1999 to 2014 along the 132°20′ E and 134°00′ E longitudes, were chosen to determine the interannual variability of the sea’s hydrochemical parameters (DO, pH, and TA—the total alkalinity phosphates, nitrate, and silicates). To limit the effects of seasonal and spatial variability, only data obtained in the warm period were used. Additionally, all data from depths shallower than 500 m were discarded because they are affected by high natural variability, mostly due to strong mesoscale dynamic structures. Our results demonstrated that the pH and DO concentrations measured in the Upper Japan Sea Proper Water (750 m), Lower Japan Sea Proper Water (1250, 1750, 2250 m), and Bottom Water (3000 m) have been decreasing in recent years. On the other hand, calculated normalized dissolved inorganic carbon (NDIC), CO2 partial pressure (pCO2), and measured nutrient concentrations have been increasing. Maximum rates of acidification and deoxygenation are occurring at around 750 m. The annual rate of increase of pCO2 in the water exceeds the atmospheric rate more than 2-fold at a depth of 750 m. The observed variability of the hydrochemical properties can be explained by the combination of the slowdown ventilation of the vertical water column and eutrophication. However, the results obtained here are valid for the subpolar region of the JES, not for the whole sea. The synchronization of the deoxygenation of the open part of the JES and PGB has been found.

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Cleavage of calcitic CaCO3 during dissolution in aqueous solution

Calcite cleavage was observed using a device to accelerate the formation and dissolution of calcitic CaCO3 by acidification in aqueous solutions. Scanning electron microscopy showed that crystals formed within 1 day and dissolution began at 3 days of aging. In the X-ray diffraction pattern, calcite was predominantly formed but an amorphous phase did not exist, even after 12 days of aging. In the diffraction pattern and lattice images obtained using a series of high-resolution transmission electron microscopy analyses, cleavages mainly occurred in the {101̅1} plane and some cleavages were observed through the {101̅4} plane.

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