Posts Tagged 'chemistry'

Seasonal controls of the carbon biogeochemistry of a fringing coral reef in the Gulf of California, Mexico

The surface of the ocean has absorbed one-third of the CO2gas that has been released by anthropogenic activities, which has resulted in a reduction in pH and the aragonite saturation state (Ωara) with potential negative impacts in calcifying organisms, such as corals. To evaluate these effects, the natural variability present must first be understood, including that of processes that operate at diurnal, seasonal, and interannual frequencies. The objective of this study was to determine the influence of physical and biogeochemical processes on the seasonal variability of the CO2-system in a fringe coral reef of the Eastern Tropical Pacific (ETP). To achieve this, a SeapHOx sensor was installed to measure temperature, salinity, dissolved oxygen, and pHTot at 30-min intervals from November 2013 (early winter) to July 2014 (early summer). The recorded temperature and salinity data fed a mixing model to identify the water masses present in the reef. We show how physical and biogeochemical oceanic processes influence and control the variability of the carbonate system. The presence of water masses with different carbon chemistries responded to two scenarios: (1) seasonal circulation on the order of months and (2) an intermittence between water masses related to mesoscale structures (eddies) on the order of weeks. A low-pH and Ωara condition was detected during summer, which was related to the presence of warm and respired Tropical Surface Water. The broadest changes in Ωara were the result of physical processes (winter ΔΩara = 0.14 and summer ΔΩara = 0.34 units) and corresponded to the transition between water masses with different carbon-biogeochemistry signals. Our results suggest that the Cabo Pulmo coral community develops in an environment with a wide range of pH and Ωara conditions and that seasonal changes are controlled by open ocean carbon biogeochemistry.

Continue reading ‘Seasonal controls of the carbon biogeochemistry of a fringing coral reef in the Gulf of California, Mexico’

Drivers of biogeochemical variability in a central California kelp forest: implications for local amelioration of ocean acidification

Kelp forests are among the world’s most productive marine ecosystems, and they have the potential to locally ameliorate ocean acidification (OA). In order to understand the contribution of kelp metabolism to local biogeochemistry, we must first quantify the natural variability and the relative contributions of physical and biological drivers to biogeochemical changes in space and time. We deployed an extensive instrument array in Monterey Bay, CA, inside and outside of a kelp forest to assess the degree to which giant kelp (Macrocystis pyrifera) locally ameliorates present‐day acidic conditions which we expect to be exacerbated by OA. Temperature, pH, and O2 variability occurred at semidiurnal, diurnal (tidal and diel), and longer upwelling event periods. Mean conditions were driven by offshore wind forcing and the delivery of upwelled water via nearshore internal bores. While near surface pH and O2 were similar inside and outside the kelp forest, surface pH was elevated inside the kelp compared to outside, suggesting that the kelp canopy locally increased surface pH. We observed the greatest acidification stress deeper in the water column where pCO2 reached levels as high as 1300 μatm and aragonite undersaturation (ΩAr <1) occurred on several occasions. At this site, kelp canopy modification of seawater properties, and thus any ameliorating effect against acidification is greatest in a narrow band of surface water. The spatial disconnect between stress exposure at depth and reduction of acidification stress at the surface warrants further assessment of utilizing kelp forests as provisioners of local OA mitigation.

Continue reading ‘Drivers of biogeochemical variability in a central California kelp forest: implications for local amelioration of ocean acidification’

Ghost factors of laboratory carbonate chemistry are haunting our experiments

For many historical and contemporary experimental studies in marine biology, seawater carbonate chemistry remains a ghost factor, an uncontrolled, unmeasured, and often dynamic variable affecting experimental organisms or the treatments to which investigators subject them. We highlight how environmental variability, such as seasonal upwelling and biological respiration, drive variation in seawater carbonate chemistry that can influence laboratory experiments in unintended ways and introduce a signal consistent with ocean acidification. As the impacts of carbonate chemistry on biochemical pathways that underlie growth, development, reproduction, and behavior become better understood, the hidden effects of this previously overlooked variable need to be acknowledged. Here we bring this emerging challenge to the attention of the wider community of experimental biologists who rely on access to organisms and water from marine and estuarine laboratories and who may benefit from explicit considerations of a growing literature on the pervasive effects of aquatic carbonate chemistry changes.

Continue reading ‘Ghost factors of laboratory carbonate chemistry are haunting our experiments’

Rapid shifts in circulation and biogeochemistry of the Southern Ocean during deglacial carbon cycle events

The Southern Ocean plays a crucial role in regulating atmospheric CO2 on centennial to millennial time scales. However, observations of sufficient resolution to explore this have been lacking. Here, we report high-resolution, multiproxy records based on precisely dated deep-sea corals from the Southern Ocean. Paired deep (∆14C and δ11B) and surface (δ15N) proxy data point to enhanced upwelling coupled with reduced efficiency of the biological pump at 14.6 and 11.7 thousand years (ka) ago, which would have facilitated rapid carbon release to the atmosphere. Transient periods of unusually well-ventilated waters in the deep Southern Ocean occurred at 16.3 and 12.8 ka ago. Contemporaneous atmospheric carbon records indicate that these Southern Ocean ventilation events are also important in releasing respired carbon from the deep ocean to the atmosphere. Our results thus highlight two distinct modes of Southern Ocean circulation and biogeochemistry associated with centennial-scale atmospheric CO2 jumps during the last deglaciation.

Continue reading ‘Rapid shifts in circulation and biogeochemistry of the Southern Ocean during deglacial carbon cycle events’

OceanSODA-ETHZ: A global gridded data set of the surface ocean carbonate system for seasonal to decadal studies of ocean acidification

Ocean acidification has altered the ocean’s carbonate chemistry profoundly since preindustrial times, with potentially serious consequences for marine life. Yet, no long-term global observation-based data set exists that permits to study changes in ocean acidification for all carbonate system parameters over the last few decades. Here, we fill this gap and present a methodologically consistent global data set of all relevant surface ocean parameters, i.e., dissolved inorganic carbon (DIC), total alkalinity (TA), partial pressure of CO2 (pCO2), pH, and the saturation state with respect to mineral CaCO3 (Ω) at monthly resolution over the period 1985 through 2018 at a spatial resolution of 1 × 1°. This data set, named OceanSODA-ETHZ, was created by extrapolating in time and space the surface ocean observations of pCO2 (from the Surface Ocean CO2 ATlas (SOCAT)) and total alkalinity (TA, from the Global Ocean Data Analysis Project (GLODAP)) using the newly developed Geospatial Random Cluster Ensemble Regression (GRaCER) method. This method is based on a two-step (cluster-regression) approach, but extends it by considering an ensemble of such cluster-regressions, leading to higher robustness. Surface ocean DIC, pH, and Ω were then computed from the globally mapped pCO2 and TA using the thermodynamic equations of the carbonate system. For the open ocean, the cluster regression method estimates pCO2 and TA with global near-zero biases and root mean squared errors of 12 µatm and 13 µmol kg−1, respectively. Taking into account also the measurement and representation errors, the total error increases to 14 µatm and 21 µmol kg−1, respectively. We assess the fidelity of the computed parameters by comparing them to direct observations from GLODAP, finding surface ocean pH and DIC global biases of near zero, and root mean squared errors of 0.023 and 16 µmol kg−1, respectively. These errors are very comparable to those expected by propagating the total errors from pCO2 and TA through the thermodynamic computations, indicating a robust and conservative assessment of the errors. We illustrate the potential of this new dataset by analyzing the climatological mean seasonal cycles of the different parameters of the surface ocean carbonate system, highlighting their commonalities and differences. The OceanSODA-ETHZ data can be downloaded from https://doi.org/10.25921/m5wx-ja34 (Gregor and Gruber, 2020).

Continue reading ‘OceanSODA-ETHZ: A global gridded data set of the surface ocean carbonate system for seasonal to decadal studies of ocean acidification’

Glacial drivers of marine biogeochemistry indicate a future shift to more corrosive conditions in an Arctic fjord

A detailed survey of a high Arctic glacier fjord (Kongsfjorden, Svalbard) was carried out in summer 2016, close to the peak of the meltwater season, in order to identify the effects of glacier runoff on nutrient distributions and the carbonate system. Short‐term weather patterns were found to exert a strong influence on freshwater content within the fjord. Freshwater inputs from glacier runoff and ice meltwater averaged (±SD) low nitrate (1.85±0.47 μM; 0.41±0.99 μM), orthophosphate (0.07±0.27 μM; 0.02 ±0.03 μM), dissolved organic carbon (27 ±14 μM in glacier runoff), total alkalinity (708±251 μmol kg‐1; 173±121 μmol kg‐1) and dissolved inorganic carbon (622±108 μmol kg‐1; 41±88 μmol kg‐1), as well as a modest silicate concentration (3.71±0.02 μM; 3.16±5.41 μM). pCO2 showed a non‐conservative behavior across the estuarine salinity gradient with a pronounced under‐saturation in the inner‐fjord, leading to strong CO2 uptake from the atmosphere. The combined effect of freshwater dilution and atmospheric CO2 absorption was the lowering of aragonite saturation state, to values that are known to negatively affect marine calcifiers (ΩAr, 1.07). Glacier discharge was therefore a strong local amplifier of ocean acidification. Future increases in discharge volume and the loss of marine productivity following the retreat of marine‐terminating glaciers inland are both anticipated to further lower ΩAr within inner‐fjord surface waters. This shift may be partially buffered by an increase in the mean freshwater total alkalinity as the fractional importance of iceberg melt to freshwater fjord inputs declines and runoff increases.

Continue reading ‘Glacial drivers of marine biogeochemistry indicate a future shift to more corrosive conditions in an Arctic fjord’

Evolution of deep-sea sediments across the Paleocene-Eocene and Eocene-Oligocene boundaries

The composition and distribution of deep-sea sediments is the result of a multitude of climatic, biotic and oceanic conditions relating to biogeochemical cycles and environmental change. Here we utilize the extensive sediment archives of the International Ocean Discovery Program (IODP) and its predecessors to construct maps of deep-sea sediment type across two critical but contrasting boundaries in the Paleogene, one characterised by an interval of extreme warmth (Paleocene/Eocene) and the other by global cooling (Eocene/Oligocene). Ocean sediment distribution shows significant divergence both between the latest Paleocene and Paleocene Eocene Thermal Maximum (PETM), across the Eocene-Oligocene Transition (EOT), and in comparison to modern sediment distributions. Carbonate sedimentation in the latest Paleocene extends to high southern latitudes. Disappearance of carbonate sediments at the PETM is well documented and can be attributed to dissolution caused by significant ocean acidification as a result of carbon-cycle perturbation. Biosiliceous sediments are rare and it is posited that the reduced biogenic silica deposition at the equator is commensurate with an overall lack of equatorial upwelling in the early Paleogene ocean. In the Southern Ocean, we attribute the low in biosiliceous burial, to the warm deep water temperatures which would have impacted biogenic silica preservation. In the late Eocene, our sediment depositional maps record a tongue of radiolarian ooze in the eastern equatorial Pacific. Enhanced biosiliceous deposits in the late Eocene equatorial Pacific and Southern Ocean are due to increased productivity and the spin-up of the oceans. Our compilation documents the enhanced global carbonate sedimentation in the early Oligocene, confirming that the drop in the carbonate compensation depth was global.

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Diel vertical migration into anoxic and high-pCO2 waters: acoustic and net-based krill observations in the Humboldt Current

A select group of marine organisms can enter the Oxygen Minimum Zones (OMZs) and even anoxic waters, while performing diel vertical migration (DVM). DVM of the euphausiid Euphausia eximia off northern Chile in the spring of 2015 was documented based on acoustic measurements using an echo sounder along with net samplings. Dissolved oxygen (DO) concentrations were obtained using a vertical profiler, and water samples were collected to obtain in situ nitrite (NO2) concentrations as well as pHT, total alkalinity (AT), and therefore carbon dioxide partial pressure (pCO2) was estimated. Krill were found to migrate up to the surface (0–50 m) during the night and returned to ca. 200–300 m depth during the day, spending between 11 and 14 h at these layers. At the surface, DO and NO2 concentrations were 208 and 0.14 μM respectively, while pHT was 8.04 and 405 μatm pCO2. In contrast, at the deeper layers (200–300 m), DO and NO2 were < 3 and 6.3 μM respectively, with pHT 7.53 and 1490 μatm pCO2. The pHT and high pCO2 values at depths represent the conditions predicted for open ocean waters in a worst-case global warming scenario by 2150. The acoustic scatter suggested that > 60% of the krill swarms enter the OMZ and anoxic waters during the daytime. These frequent migrations suggest that krill can tolerate such extreme conditions associated with anoxic and high-pCO2 waters. The inferences drawn from the observation of these migrations might have strong implications for the current oceanic carbon pump models, highlighting the need for understanding the molecular and physiological adaptations allowing these migrations.

Continue reading ‘Diel vertical migration into anoxic and high-pCO2 waters: acoustic and net-based krill observations in the Humboldt Current’

Benthic respiration in hypoxic waters enhances bottom water acidification in the northern Gulf of Mexico

It is known that surface water eutrophication enhances bottom water ocean acidification via respiration in coastal oceans. However, the role of benthic processes in influencing bottom water acidification has not been sufficiently explored. We examined this issue by analyzing a 10‐year summer carbonate chemistry dataset in bottom water together with recent benthic flux measurements and literature benthic flux data in the northern Gulf of Mexico. The difference between the observed and estimated pH (Ω) values calculated from anthropogenic CO2 increase and water column aerobic respiration were defined as ΔpH (ΔΩ). We found that ΔpH and ΔΩ values in hypoxic condition were −0.03 ± 0.04 (mean ± standard deviation) and −0.15 ± 0.39, respectively. Both ΔpH and ΔΩ values in hypoxic conditions were significantly lower than zero (p < 0.05). The net results of anaerobic respiration, oxidation of reduced chemcials, burial of iron sulfide minerals, and possible CaCO3 dissolution may have led to an alkalinity to DIC production ratio of less than 1 in porewater. This caused the ratio of alkalinity to dissolved inorganic carbon fluxes from sediment to bottom water to be less than 1, which led to additional bottom water acidification. Our analysis and model simulations demonstrate that severe hypoxic and anoxic conditions, which correspond to less water movement, favor the accumulation of benthic respiration products, leading to additional pH and Ω reductions. The findings on sediment processes contributing to acidification in bottom waters provide new insights into the sensitivity of coastal ocean acidification to low‐oxygen conditions under current and future climates and anthropogenic nutrient loading scenarios.

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Physical and biogeochemical drivers of alongshore pH and oxygen variability in the California Current System

In the California Current System (CCS), the nearshore environment experiences natural exposure to low pH and reduced oxygen in response to coastal upwelling. Anthropogenic impacts further decrease pH and oxygen below biological thresholds, making the CCS particularly vulnerable to ocean acidification and hypoxia. Results from a coupled physical‐biogeochemical model reveal a strongly heterogeneous alongshore pattern of nearshore pH and oxygen in the central CCS, both in their long‐term means and trends. This spatial structuring is explained by an interplay between alongshore variability in local upwelling intensity and subsequent primary production, modulated by nearshore advection and regional geostrophic currents. The model solution suggests that the progression of ocean acidification and hypoxia will not be spatially homogeneous, thereby highlighting the need to consider subregional processes when assessing natural and anthropogenic impacts on coastal ecosystems in eastern boundary current upwelling regions.

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