Undersaturated Seawater Research Articles

Coherent tracer correlations in deep-sea corals and implications for biomineralization mechanisms underlying vital effects

Deep-sea corals are a useful archive of thermocline, intermediate, and deep waters in past oceans. However, application of traditional oceanographic tracers to deep-sea corals remains a challenge due to our insufficient understanding of their “vital effects”. Deep-sea corals are ideal test organisms to study the mechanism underlying vital effects generally, due to the large tracer gradients in individual corals living under relatively constant environmental conditions. Lessons learned from these corals might apply to other scleractinia and to marine calcifiers more generally. Here we present stable isotope, minor and trace metal (Me/Ca ratios) data in a suite of modern Desmophyllum dianthus specimens, collected over multiple spatial scales in individual corals (bulk, micromill, SIMS, NanoSIMS), with multi-proxy analyses made on the same material whenever possible. Spatially coherent Me/Ca correlations are observed in the fibrous aragonite of individual corals, including positive correlations between Mg/Ca, Li/Ca and B/Ca, as well as negative correlations between Mg/Ca and Sr/Ca, consistent with previous studies. We also for the first time document strong correlations between the isotopic (δ18O and δ13C) and elemental compositions of the skeletons, most notably a negative correlation between δ18O and Mg/Ca. The centers of calcification (COCs) in the coral skeletons show distinct tracer correlations from the aragonite fibers that possibly reflect a more complicated formation mechanism. We interpret the spatially coherent tracer correlations in deep-sea corals with a numerical model of coral calcification previously developed for stable isotopes that considers the role of the enzyme carbonic anhydrase in the calcification processs. With the carbonate chemistry in the model constrained by the stable isotope data, we are able to explain the observed Me/Ca correlations as well as their range of variability, as a result of internal pH elevation in the extracellular calcifying fluid (ECF) of the corals with limited Ca-pumping through the calicoblastic membrane. In particular, the positive Mg/Ca–B/Ca correlation in the fibrous aragonite suggests a borate (B(OH)4–) substitution for carbonate ion (CO32–) incorporation mechanism in biogenic aragonite. We also suggest the growth rate dependence of the incorporation of minor and trace elements based conceptually on an ion-by-ion growth model may help explain the absolute Me/Ca values in biogenic aragonites. Finally, we generally find more limited tracer variability in corals from undersaturated seawater compared to their counterparts from supersaturated conditions, suggesting a limit to their internal pH elevation in response to this environmental stress. Understanding the biomineralization mechanisms underlying the vital effects is important for better use of these tracers for paleoceanographic applications, and may shed light on the response of marine calcification to future ocean acidification.

Barium bioaccumulation by bacterial biofilms and implications for Ba cycling and use of Ba proxies

Ba proxies have been broadly used to reconstruct past oceanic export production. However, the precise mechanisms underlying barite precipitation in undersaturated seawater are not known. The link between bacterial production and particulate Ba in the ocean suggests that bacteria may play a role. Here we show that under experimental conditions marine bacterial biofilms, particularly extracellular polymeric substances (EPS), are capable of bioaccumulating Ba, providing adequate conditions for barite precipitation. An amorphous P-rich phase is formed at the initial stages of Ba bioaccumulation, which evolves into barite crystals. This supports that in high productivity regions where large amounts of organic matter are subjected to bacterial degradation, the abundant EPS would serve to bind the necessary Ba and form nucleation sites leading to barite precipitation. This also provides new insights into barite precipitation and opens an exciting field to explore the role of EPS in mineral precipitation in the ocean.

Cidaroids spines facing ocean acidification

When facing seawater undersaturated towards calcium carbonates, spines of classical sea urchins (euechinoids) show traces of corrosion although they are covered by an epidermis. Cidaroids (a sister clade of euechinoids) are provided with mature spines devoid of epidermis, which makes them, at first sight, more sensitive to dissolution when facing undersaturated seawater. A recent study showed that spines of a tropical cidaroid are resistant to dissolution due to the high density and the low magnesium concentration of the peculiar external spine layer, the cortex. The biofilm and epibionts covering the spines was also suggested to take part in the spine protection. Here, we investigate the protective role of these factors in different cidaroid species from a broad range of latitude, temperature and depth. The high density of the cortical layer and the cover of biofilm and epibionts were confirmed as key protection against dissolution. The low magnesium concentration of cidaroid spines compared to that of euechinoid ones makes them less soluble in general.

Benthic marine calcifiers coexist with CaCO3‐undersaturated seawater worldwide

AbstractOcean acidification and decreasing seawater saturation state with respect to calcium carbonate (CaCO3) minerals have raised concerns about the consequences to marine organisms that build CaCO3 structures. A large proportion of benthic marine calcifiers incorporate Mg2+ into their skeletons (Mg‐calcite), which, in general, reduces mineral stability. The relative vulnerability of some marine calcifiers to ocean acidification appears linked to the relative solubility of their shell or skeletal mineralogy, although some organisms have sophisticated mechanisms for constructing and maintaining their CaCO3 structures causing deviation from this dependence. Nevertheless, few studies consider seawater saturation state with respect to the actual Mg‐calcite mineralogy (ΩMg‐x) of a species when evaluating the effect of ocean acidification on that species. Here, a global dataset of skeletal mole % MgCO3 of benthic calcifiers and in situ environmental conditions spanning a depth range of 0 m (subtidal/neritic) to 5600 m (abyssal) was assembled to calculate in situ ΩMg‐x. This analysis shows that 24% of the studied benthic calcifiers currently experience seawater mineral undersaturation (ΩMg‐x < 1). As a result of ongoing anthropogenic ocean acidification over the next 200 to 3000 years, the predicted decrease in seawater mineral saturation will expose approximately 57% of all studied benthic calcifying species to seawater undersaturation. These observations reveal a surprisingly high proportion of benthic marine calcifiers exposed to seawater that is undersaturated with respect to their skeletal mineralogy, underscoring the importance of using species‐specific seawater mineral saturation states when investigating the impact of CO2‐induced ocean acidification on benthic marine calcification.

Maintained larval growth in mussel larvae exposed to acidified under-saturated seawater.

Ocean acidification (OA) is known to affect bivalve early life-stages. We tested responses of blue mussel larvae to a wide range of pH in order to identify their tolerance threshold. Our results confirmed that decreasing seawater pH and decreasing saturation state increases larval mortality rate and the percentage of abnormally developing larvae. Virtually no larvae reared at average pHT 7.16 were able to feed or reach the D-shell stage and their development appeared to be arrested at the trochophore stage. However larvae were capable of reaching the D-shell stage under milder acidification (pHT ≈ 7.35, 7.6, 7.85) including in under-saturated seawater with Ωa as low as 0.54 ± 0.01 (mean ± s. e. m.), with a tipping point for normal development identified at pHT 7.765. Additionally growth rate of normally developing larvae was not affected by lower pHT despite potential increased energy costs associated with compensatory calcification in response to increased shell dissolution. Overall, our results on OA impacts on mussel larvae suggest an average pHT of 7.16 is beyond their physiological tolerance threshold and indicate a shift in energy allocation towards growth in some individuals revealing potential OA resilience.

IMPACT OF CHANGING CARBONATE CHEMISTRY, TEMPERATURE, AND SALINITY ON GROWTH AND TEST DEGRADATION OF THE BENTHIC FORAMINIFER AMMONIA AOMORIENSIS

The present study investigated the combined effects of ocean acidification, temperature, and salinity on growth and test degradation of Ammonia aomoriensis. This species is one of the dominant benthic foraminifera in near-coastal habitats of the southwestern Baltic Sea that can be particularly sensitive to changes in seawater carbonate chemistry. To assess potential responses to ocean acidification and climate change, we performed a fully crossed experiment involving three temperatures (8, 13, and 18uC), three salinities (15, 20, and 25) and four pCO2 levels (566, 1195, 2108, and 3843 matm) for six weeks. Our results highlight a sensitive response of A. aomoriensis to undersaturated seawater with respect to calcite. The specimens continued to grow and increase their test diameter in treatments with pCO2 ,1200 matm, when Vcalc .1. Growth rates declined when pCO2 exceeded 1200 matm (Vcalc ,1). A significant reduction in test diameter and number of tests due to dissolution was observed below a critical Vcalc of 0.5. Elevated temperature (18uC) led to increased Vcalc, larger test diameter, and lower test degradation. Maximal growth was observed at 18uC. No significant relationship was observed between salinity and test growth. Lowered and undersaturated Vcalc, which results from increasing pCO2 in bottom waters, may cause a significant future decline of the population density of A. aomoriensis in its natural environment. At the same time, this effect might be partially compensated by temperature rise due to global warming.

A natural hydrate dissolution experiment on complex multi-component hydrates on the sea floor

Dissolution of natural hydrate cores was measured using time-lapse photography on the seafloor at Barkley Canyon (850 m depth and 4.17 °C). Two types of hydrate fabrics in close contact with one another were studied: a “yellow” hydrate stained with condensate oil and a “white” hydrate. From thermogenic origins, both fabrics contained methane as well as heavier hydrocarbons. These multi-component hydrates were calculated to be well within p– T stability conditions (<200 m water depth needed at 4.17 °C). While stable in pressure and temperature, the hydrates were bathed in under-saturated seawater, which promoted dissolution. The flux of gas from the shrinking yellow hydrate core was 0.15 ± 0.01 mmol gas/m 2 s, while the white hydrate dissolved faster at 0.25 ± 0.02 mmol gas/m 2 s. To determine the controlling mechanism for the observed changes in the hydrate cores, experimental results were compared with an engineering correlation for convective mass transfer. Using water velocity as a fitting parameter, the correlation agreed well with results from a previous dissolution experiment on well-characterized synthetic hydrates. Even with a number of other unknowns, when applied to the natural hydrate, the mass transfer correlation predicted the dissolution rate within 20%. This seafloor-based experiment, along with visual observations of seafloor hydrate dissolution over a 3-day period, were used to further understand the fate of natural seafloor hydrates exposed on the seafloor. By showing that mass transfer is the rate-controlling mechanism for dissolution of these natural hydrate outcrops, proper hydrodynamic calculations can be employed to give a refined estimate on hydrate dissolution rates.

Methane hydrate dissolution rates in undersaturated seawater under controlled hydrodynamic forcing

The dissolution of in-situ generated methane hydrate in undersaturated, synthetic seawater ( S = 35) was investigated in a series of laboratory-based experiments at P-/ T-conditions within the hydrate stability field. A controlled flow field was generated across the smooth hydrate surface to test if, in addition to thermodynamic variables, the dissolution rate is influenced by changing hydrodynamic conditions. The dissolution rate was found to be strongly dependent on the friction velocity, showing that hydrate dissolution in undersaturated seawater is a diffusion-controlled process. The experimental data was used to obtain diffusional mass transfer coefficients k d, which were found to correlate linearly with the friction velocity, u ★. The resulting k d/ u ★-correlation allows predicting the flux of methane from natural gas hydrate exposures at the sediment/seawater interface into the bulk water for a variety of natural P, T and flow conditions. It also is a tool for estimating the rate of hydrate regrowth at locations where natural hydrate outcrops at the seafloor persist in contact with undersaturated seawater.

Morphological and compositional changes in the skeletons of new coral recruits reared in acidified seawater: Insights into the biomineralization response to ocean acidification

We reared primary polyps (new recruits) of the common Atlantic golf ball coral Favia fragum for 8 days at 25°C in seawater with aragonite saturation states ranging from ambient (Ω = 3.71) to strongly undersaturated (Ω = 0.22). Aragonite was accreted by all corals, even those reared in strongly undersaturated seawater. However, significant delays, in both the initiation of calcification and subsequent growth of the primary corallite, occurred in corals reared in treatment tanks relative to those grown at ambient conditions. In addition, we observed progressive changes in the size, shape, orientation, and composition of the aragonite crystals used to build the skeleton. With increasing acidification, densely packed bundles of fine aragonite needles gave way to a disordered aggregate of highly faceted rhombs. The Sr/Ca ratios of the crystals, measured by SIMS ion microprobe, increased by 13%, and Mg/Ca ratios decreased by 45%. By comparing these variations in elemental ratios with results from Rayleigh fractionation calculations, we show that the observed changes in crystal morphology and composition are consistent with a &gt;80% decrease in the amount of aragonite precipitated by the corals from each “batch” of calcifying fluid. This suggests that the saturation state of fluid within the isolated calcifying compartment, while maintained by the coral at levels well above that of the external seawater, decreased systematically and significantly as the saturation state of the external seawater decreased. The inability of the corals in acidified treatments to achieve the levels of calcifying fluid supersaturation that drive rapid crystal growth could reflect a limit in the amount of energy available for the proton pumping required for calcification. If so, then the future impact of ocean acidification on tropical coral ecosystems may depend on the ability of individuals or species to overcome this limitation and achieve the levels of calcifying fluid supersaturation required to ensure rapid growth.

An increasing CO2 sink in the Arctic Ocean due to sea‐ice loss

The Arctic Ocean and adjacent continental shelf seas such as the Chukchi and Beaufort Seas are particularly sensitive to long‐term change and low‐frequency modes of atmosphere‐ocean‐sea‐ice forcing. The cold, low salinity surface waters of the Canada Basin of the Arctic Ocean are undersaturated with respect to CO2 in the atmosphere and the region has the potential to take up atmospheric CO2, although presently suppressed by sea‐ice cover. Undersaturated seawater CO2 conditions of the Arctic Ocean are maintained by export of water with low dissolved inorganic carbon content and modified by intense seasonal shelf primary production. Sea‐ice extent and volume in the Arctic Ocean has decreased over the last few decades, and we estimate that the Arctic Ocean sink for CO2 has tripled over the last 3 decades (24 Tg yr−1 to 66 Tg yr−1) due to sea‐ice retreat with future sea‐ice melting enhancing air‐to‐sea CO2 flux by ∼28% per decade.

Dissolution rates of pure methane hydrate and carbon-dioxide hydrate in undersaturated seawater at 1000-m depth

To help constrain models involving the chemical stability and lifetime of gas clathrate hydrates exposed at the seafloor, dissolution rates of pure methane and carbon-dioxide hydrates were measured directly on the seafloor within the nominal pressure-temperature (P/T) range of the gas hydrate stability zone. Other natural boundary conditions included variable flow velocity and undersaturation of seawater with respect to the hydrate-forming species. Four cylindrical test specimens of pure, polycrystalline CH 4 and CO 2 hydrate were grown and fully compacted in the laboratory, then transferred by pressure vessel to the seafloor (1028 m depth), exposed to the deep ocean environment, and monitored for 27 hours using time-lapse and HDTV cameras. Video analysis showed diameter reductions at rates between 0.94 and 1.20 μm/s and between 9.0 and 10.6 · 10 −2 μm/s for the CO 2 and CH 4 hydrates, respectively, corresponding to dissolution rates of 4.15 ± 0.5 mmol CO 2/m 2s and 0.37 ± 0.03 mmol CH 4/m 2s. The ratio of the dissolution rates fits a diffusive boundary layer model that incorporates relative gas solubilities appropriate to the field site, which implies that the kinetics of the dissolution of both hydrates is diffusion-controlled. The observed dissolution of several mm (CH 4) or tens of mm (CO 2) of hydrate from the sample surfaces per day has major implications for estimating the longevity of natural gas hydrate outcrops as well as for the possible roles of CO 2 hydrates in marine carbon sequestration strategies.

Diminished efficiency in the oceanic silica pump caused by bacteria‐mediated silica dissolution

Previous laboratory findings indicated that marine bacteria accelerate biogenic silica (bSiO2) dissolution rates in the sea by degrading the organic coating surrounding diatom frustules and exposing the underlying silica to chemical attack by undersaturated seawater. We examined the effectiveness of bacterial activity in facilitating in situ bSiO2 dissolution during a diatom bloom in Monterey Bay, California, following moderate upwelling. Inhibition of bacterial activity with antibiotics and protease inhibitors reduced specific bSiO2 dissolution rates (Vdis) at five of six stations, with a reduction of 44 ± 27% (mean ± SD, n = 6, range 22–91%) over 24 h. Reduced Vdis in inhibitor treatments corresponded with reductions in abundance, production, and proteolytic activity of attached bacteria. Dissolution rates were highly correlated with protease activity integrated from the surface down to the depth where each dissolution was measured, suggesting that increased Vdis with depth in the upper 20–80 m of the ocean is caused by the progressive removal of organic matter from frustules during sinking. Facilitation of bSiO2 dissolution by in situ bacterial assemblages varied between stations and was likely influenced by the physiological condition of resident diatom assemblages. Denaturing gradient gel electrophoresis and 16S rRNA gene sequencing of bacteria colonizing in situ diatom assemblages confirmed previous findings that specific bacterial phylotypes (Cytophaga/Flavobacteria/Bacteriodes; a and g subclasses of Proteobacteria) mediate bSiO2 dissolution.

Ultrastructure, dissolution and "pyritization" of Late Quaternary and Recent echinoderms

The diagenetic history of the skeletal elements of Late Pleistocene-Holocene Ophiura sarsi from the shelf off northern Norway (Andfjorden, Malangsdjupet) is elucidated by comparison with natural and induced degradation of the skeletal elements of Recent ophiuroids (brittle stars) and asteroids (sea stars) from Danish waters. Dissolution features ("core-and-rind") in the trabeculae of fossil and Recent echinoderm stereom are initiated during death and early decay of organic tissue in the animals. The trabeculae have a polycrystal­line lamellar ultrastructure and lose their older central part during later stages of dissolution, which are dependant on undersaturation of the sea-water with regard to CaC03• The presence of undersaturated sea-water is supported by palaeoecological studies (Thomsen &amp; Vorren 1984, 1986) implying oxygen deficient periods in the Late Pleistocene and an increased biogenic production in the Holocene. Pyrite framboids are situated in the secondary voids within the trabeculae and in the pore space of the stereom of the Late Pleistocene elements. No pyrite is observed within the polycrystalline lamellar ultrastructure of the trabeculae. The Late Pleistocene "pyritization" took place during oxygen deficient periods at the sediment-water interface or within the reduced zone of the topmost sediment.

Water column dissolution of aragonite in the Pacific Ocean

Pelagic pteropods are an important component of the oceanic CO2 system. Their shells appear to be a principal source of excess alkalinity in the upper water column of the North Pacific Ocean. Dissolution of aragonite must therefore be taken account of in generating models of the oceanic CO2 system and is also an important cause of sample loss from long-term sediment traps deployed in undersaturated seawater.

Physical Chemistry of Carbonates in Oceans: ABSTRACT

The common carbonate minerals found in oceanic sediments are aragonite and high and low magnesium varieties of calcite. A large proportion of deep seawater is undersaturated with respect to all three. This conclusion is based on laboratory studies of the effects of temperature and pressure on carbonate equilibria in seawater combined with shipboard measurements of water properties as well as upon actual measurements of dissolution rates of calcium carbonate samples held at various depth. Undersaturation is caused by biologic production of CO2 at shallower depths and by the effect of increased pressure at greater depths on the solubility of CaCO3. The so-called below which CaCO3 disappears from deep sea sediments does n t represent simply a downward change from supersaturated to undersaturated water. This is proved by the presence of undersaturated water above the compensation depth and by the fact that the compensation depth may be thousands of meters below the depth where CaCO3 begins to disappear from the sediments; i.e., there is a zone of disappearance and not a single sharply defined depth. The rate of dissolution of CaCO3 in undersaturated seawater is slowed by dissolved Mg and by dissolved organic matter and this helps account for the lack of dissolution where it is expected to occur. Surface seawater, in contrast to deep water, is generally supersaturated with respect to both calcite and aragonite. However, inorganic precipitation rarely occurs due to the inhibiting effects of Mg++ and organic matter as dissolved species and as surface coatings on mineral grains. End_of_Article - Last_Page 331------------