Posts Tagged 'chemistry'

Chemical characterization of Punta de Fuencaliente CO2 seeps system (La Palma Island, NE Atlantic Ocean): a new natural laboratory for ocean acidification studies

We present a new natural carbon dioxide (CO2) system located off the southern coast of La Palma Island (Canary Islands, Spain). Like others CO2 seeps, these seeps can be used as an analogue to study the effects of ocean acidification (OA) on the marine realm. With this aim, we present an accurate chemical characterization of the seeps system carbon emissions, describing the carbon system dynamics, by measuring pH, AT and CT, as well as, Ω aragonite and calcite. Our explorations on the area have found several emission points with similar chemical features. Here, the CO2 emission flux varies between 2.8 kg CO2 d−1 to 28 kg CO2 d−1, becoming a significant source of carbon. CO2 seeps are of volcanic origin and the alteration of local ocean chemistry is due to acid brackish water discharges. Although this kind of acidified system is not a perfect image of future oceans, this area of La Palma island is an exceptional spot to perform studies aimed to understand the effect of different levels of OA on the functioning of marine ecosystems. These studies can then be used to comprehend how life has persisted through past Eras, with higher atmospheric CO2, or to predict the consequences of present fossil fuel usage on the marine ecosystem of the future oceans.

Continue reading ‘Chemical characterization of Punta de Fuencaliente CO2 seeps system (La Palma Island, NE Atlantic Ocean): a new natural laboratory for ocean acidification studies’

Current estimates of K1* and K2* appear inconsistent with measured CO2 system parameters in cold oceanic regions

Seawater absorption of anthropogenic atmospheric carbon dioxide (CO2) has led to a range of changes in carbonate chemistry, collectively referred to as ocean acidification. Stoichiometric dissociation constants used to convert measured carbonate system variables (pH, pCO2, dissolved inorganic carbon, total alkalinity) into globally comparable parameters are crucial for accurately quantifying these changes. The temperature and salinity coefficients of these constants have generally been experimentally derived under controlled laboratory conditions. Here, we use field measurements of carbonate system variables taken from the Global Ocean Data Analysis Project version 2 and the Surface Ocean CO2 Atlas data products to evaluate the temperature dependence of the carbonic acid stoichiometric dissociation constants. By applying a novel iterative procedure to a large dataset of 948 surface-water, quality-controlled samples where four carbonate system variables were independently measured, we show that the set of equations published by Lueker et al. (2000), currently preferred by the ocean acidification community, overestimates the stoichiometric dissociation constants at temperatures below about 8 ∘C. We apply these newly derived temperature coefficients to high-latitude Argo float and cruise data to quantify the effects on surface-water pCO2 and calcite saturation states. These findings highlight the critical implications of uncertainty in stoichiometric dissociation constants for future projections of ocean acidification in polar regions and the need to improve knowledge of what causes the CO2 system inconsistencies in cold waters.

Continue reading ‘Current estimates of K1* and K2* appear inconsistent with measured CO2 system parameters in cold oceanic regions’

A 17-year dataset of surface water fugacity of CO2 along with calculated pH, aragonite saturation state and air–sea CO2 fluxes in the northern Caribbean Sea

A high-quality dataset of surface water fugacity of CO2 (fCO2w)1, consisting of over a million observations, and derived products are presented for the northern Caribbean Sea, covering the time span from 2002 through 2018. Prior to installation of automated pCO2 systems on cruise ships of Royal Caribbean International and subsidiaries, very limited surface water carbon data were available in this region. With this observational program, the northern Caribbean Sea has now become one of the best-sampled regions for pCO2 of the world ocean. The dataset and derived quantities are binned and averaged on a 1∘ monthly grid and are available at (last access: 30 June 2020) (; Wanninkhof et al., 2019a). The derived quantities include total alkalinity (TA), acidity (pH), aragonite saturation state (ΩAr) and air–sea CO2 flux and cover the region from 15 to 28∘ N and 88 to 62∘ W. The gridded data and products are used for determination of status and trends of ocean acidification, for quantifying air–sea CO2 fluxes and for ground-truthing models. Methodologies to derive the TA, pH and ΩAr and to calculate the fluxes from fCO2w temperature and salinity are described.

Continue reading ‘A 17-year dataset of surface water fugacity of CO2 along with calculated pH, aragonite saturation state and air–sea CO2 fluxes in the northern Caribbean Sea’

The recent state and variability of the carbonate system of the Canadian Arctic in the context of ocean acidification (update)

Ocean acidification driven by the uptake of anthropogenic CO2 by the surface oceans constitutes a potential threat to the health of marine ecosystems around the globe. The Arctic Ocean is particularly vulnerable to acidification and thus is an ideal region to study the progression and effects of acidification before they become globally widespread. The appearance of undersaturated surface waters with respect to the carbonate mineral aragonite (ΩA<1), an important threshold beyond which the calcification and growth of some marine organisms might be hindered, has recently been documented in the Canada Basin and adjacent Canadian Arctic Archipelago (CAA), a dynamic region with an inherently strong variability in biogeochemical processes. Nonetheless, few of these observations were made in the last 5 years and the spatial coverage in the latter region is poor. We use a dataset of carbonate system parameters measured in the CAA and its adjacent basins (Canada Basin and Baffin Bay) from 2003 to 2016 to describe the recent state of these parameters across the Canadian Arctic and investigate the amplitude and sources of the system's variability over more than a decade. Our findings reveal that, in the summers of 2014 to 2016, the ocean surface across our study area served as a net CO2 sink and was partly undersaturated with respect to aragonite in the Canada Basin and the Queen Maud Gulf, the latter region exhibiting undersaturation over its entire water column at some locations. We estimate, using measurements made across several years, that approximately a third of the interannual variability in surface dissolved inorganic carbon (DIC) concentrations in the CAA results from fluctuations in biological activity. In consideration of the system's variability resulting from these fluctuations, we derive times of emergence of the anthropogenic ocean acidification signal for carbonate system parameters in the study area.

Continue reading ‘The recent state and variability of the carbonate system of the Canadian Arctic in the context of ocean acidification (update)’

Long-term effects of elevated CO2 on the population dynamics of the seagrass Cymodocea Nodosa: evidence from volcanic seeps

We used population reconstruction techniques to assess for the first time the population dynamics of a seagrass, Cymodocea nodosa, exposed to long-term elevated CO2 near three volcanic seeps and compare them with reference sites away from the seeps. Under high CO2, the density of shoots and of individuals (apical shoots), and the vertical and horizontal elongation and production rates, were higher. Nitrogen effects on rhizome elongation and production rates and on biomass, were stronger than CO2 as these were highest at the location where the availability of nitrogen was highest. At the seep where the availability of CO2 was highest and nitrogen lowest, density of shoots and individuals were highest, probably due to CO2 effects on shoot differentiation and induced reproductive output, respectively. In all three seeps there was higher short- and long-term recruitment and growth rates around zero, indicating that elevated CO2 increases the turnover of C. nodosa shoots.

Continue reading ‘Long-term effects of elevated CO2 on the population dynamics of the seagrass Cymodocea Nodosa: evidence from volcanic seeps’

Ocean acidification from below in the tropical Pacific

Identifying ocean acidification and its controlling mechanisms is an important priority within the broader question of understanding how sustained anthropogenic CO2 emissions are harming the health of the ocean. Through extensive analysis of observational data products for ocean inorganic carbon, here we quantify the rate at which acidification is proceeding in the western tropical Pacific Warm Pool, revealing ‐0.0013 ±0.0001 yr‐1 for pH and ‐0.0083±0.0007 yr‐1 for the saturation index of aragonite for the years 1985‐2016. However, the mean rate of total dissolved inorganic carbon increase (+0.81 ±0.06 μmol kg‐1 yr‐1) sustaining acidification was ~20% slower than what would be expected if it were simply controlled by the rate of atmospheric CO2 increase and transmitted through local air‐sea CO2 equilibration. Joint Lagrangian and Eulerian model diagnostics indicate that the acidification of the Warm Pool occurs primarily through the anthropogenic CO2 that invades the ocean in the extra‐tropics, is transported to the tropics through the thermocline shallow overturning circulation, and then re‐emerges into surface waters within the tropics through the Equatorial Undercurrent from below. An interior residence time of several years to decades, acting in conjunction with the accelerating CO2 growth in the atmosphere, can be expected to contribute to modulating the rate of Warm Pool acidification.

Continue reading ‘Ocean acidification from below in the tropical Pacific’

The characteristics of the CO2 system of the Oder River estuary (Baltic Sea)


• The CO2 system in the Oder River Estuary was investigated for the first time.

• OM production and remineralization affect the CO2 system in the Oder River Estuary.

• Extreme primary production may initiate mineral precipitation of calcite in high AT.

• Estuarine processes may modify the riverine loads of AT and CT to the Baltic Sea.


This study examined the CO2 system in the estuary of the Oder River, one of the largest rivers entering the Baltic Sea. Three measurable parameters describing the CO2 system, namely total alkalinity (AT), total CO2 (CT), and the partial pressure of CO2 (pCO2), were investigated together with dissolved oxygen, salinity (S), and temperature during two RV Oceania cruises, in May and November of 2016. Large spatial variabilities of AT (1771–2940 μmol kg−1) and CT (1676–2972 μmol kg−1) were determined along the S gradient between the open Baltic Sea and river mouth. In November, the relationships of AT–S and CT-S indicated conservative mixing whereas in May both were strongly affected by biomass production and calcium carbonate formation. The waters of the Oder were oversaturated with CO2 compared to the atmosphere, irrespective of the season, with pCO2 values of 1351 ± 42 μatm in May and 1120 ± 32 μatm in November. In the Szczecin Lagoon, however, pCO2 levels dropped significantly, to 63 μatm, in May, accompanied by an O2 saturation of up to 134% during the same period. The inverse correlation of pCO2 and O2 saturation indicated that the distribution of CO2 and O2 in the estuary at the time of sampling was controlled mostly by biological activity. The very large drop in the pCO2 of the Szczecin Lagoon induced an extreme oversaturation of CaCO3 that triggered mineral calcite precipitation. The mineral precipitation of carbonates in the lagoon may have accounted for as much as 40% of the CT depletion determined in May, with the remaining 60% attributed to the joint effect of net ecosystem production and CO2 air/water gas exchange.

Continue reading ‘The characteristics of the CO2 system of the Oder River estuary (Baltic Sea)’

Fragmented kelp forest canopies retain their ability to alter local seawater chemistry

Kelp forests support some of the most productive and diverse ecosystems on Earth, and their ability to uptake dissolved inorganic carbon (DIC) allows them to modify local seawater chemistry, creating gradients in carbon, pH, and oxygen in their vicinity. By taking up both bicarbonate and CO2 as a carbon source for photosynthesis, kelp forests can act as carbon sinks, reducing nearby acidity and increasing dissolved oxygen; creating conditions conducive to calcification. Recent stressors, however, have reduced kelp forest canopies globally; converting once large and persistent forests to fragmented landscapes of small kelp patches. In a two-year study, we determined whether fragmented kelp patches retained the ability to alter local seawater chemistry. We found that diel fluctuations of multiple parameters of carbonate chemistry were greater in the kelp canopy than in the kelp benthos and in adjacent urchin barrens, consistent with metabolic activity by the kelp. Further, kelp fragments increased pH and aragonite saturation and decreased pCO2 during the day to a similar degree as large, intact kelp forests. We conclude that small kelp patches could mitigate OA stress and serve as spatial and temporal refugia for canopy-dwelling organisms, though this effect is temporary and confined to daylight hours during the growing season.

Continue reading ‘Fragmented kelp forest canopies retain their ability to alter local seawater chemistry’

Anthropogenic nitrogen‐induced changes in seasonal carbonate dynamics in a productive coastal environment

We estimated the seasonal extremes in pH and the aragonite saturation state (Ωarag) for the Yellow Sea over the past 30 years using recent (2015–2018) carbonate datasets, along with historical datasets of surface N and bottom water dissolved O2 concentrations. The rate of increase in surface N was assumed to set the post‐bloom surface dissolved inorganic C concentration resulting from the complete utilization of N by phytoplankton, while the decrease in bottom water O2 was assumed to reflect the pre‐bloom surface C, as a consequence of C‐rich bottom water (resulting from the transport of greater amounts of organic matter from the surface) being brought to the surface. With the increasing load of anthropogenic N, the net community metabolism (an increase in organic matter production at the surface and subsequent remineralization at the seafloor) has lowered the seasonal amplitude of pH by 0.14, but increased the amplitude of Ωarag by 0.8.

Continue reading ‘Anthropogenic nitrogen‐induced changes in seasonal carbonate dynamics in a productive coastal environment’

Exploring the iron‐binding potential of the ocean using a combined pH and DOC parameterization

The major part of dissolved iron (DFe) in seawater is bound to organic matter, which prevents iron from adsorptive removal by sinking particles and essentially regulates the residence time of DFe and its availability for marine biota. Characteristics of iron‐binding ligands highly depend on their biological origin and physico‐chemical properties of seawater which may intensely alter under ongoing climate change. To understand environmental controls on the iron binding, we applied a function of pH and dissolved organic carbon (DOC) to describe changes in the binding strength of organic ligands in a global biogeochemical model (REcoM). This function was derived based on calculations using a thermodynamic chemical speciation model NICA. This parameterization considerably improved the modeled DFe distribution, particularly in the surface Pacific and the global mesopelagic and deep waters, compared to our previous model simulations with a constant ligand or one prognostic ligand. This indicates that the organic binding of iron is apparently controlled by seawater pH in addition to its link to organic matter. We tested further the response of this control to environmental changes in a simulation with future pH of a high emission scenario. The response of the binding potential shows a complex pattern in different regions and is regulated by factors that have opposite effects on the binding potential. The relative contributions of these factors can change over time by a continual change of environmental conditions. A dynamic feedback system therefore needs to be considered to predict the marine iron cycle under ongoing climate change.

Continue reading ‘Exploring the iron‐binding potential of the ocean using a combined pH and DOC parameterization’

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Ocean acidification in the IPCC AR5 WG II

OUP book