Posts Tagged 'chemistry'

The climate sensitivity of northern Greenland fjords is amplified through sea-ice damming

Record-high air temperatures were observed over Greenland in the summer of 2019 and melting of the northern Greenland Ice Sheet was particularly extensive. Here we show, through direct measurements, that near surface ocean temperatures in Sherard Osborn Fjord, northern Greenland, reached 4 °C in August 2019, while in the neighboring Petermann Fjord, they never exceeded 0 °C. We show that this disparity in temperature between the two fjords occurred because thick multi-year sea ice at the entrance of Sherard Osborn Fjord trapped the surface waters inside the fjord, which led to the formation of a warm and fresh surface layer. These results suggest that the presence of multi-year sea ice increases the sensitivity of Greenland fjords abutting the Arctic Ocean to climate warming, with potential consequences for the long-term stability of the northern sector of the Greenland Ice Sheet.

Continue reading ‘The climate sensitivity of northern Greenland fjords is amplified through sea-ice damming’

Natural CO2 seeps reveal adaptive potential to ocean acidification in fish

Volcanic CO2 seeps are natural laboratories that can provide insights into the adaptation of species to ocean acidification. Whilst many species are challenged by reduced pH levels, some species benefit from the altered environment and thrive. Here, we explore the molecular mechanisms of adaptation to ocean acidification in a population of a temperate fish species that experiences increased population sizes under elevated CO2. Fish from CO2 seeps exhibited an overall increased gene expression in gonad tissue compared to those from ambient CO2 sites. Up‐regulated genes at CO2 seeps are possible targets of adaptive selection as they can directly influence the physiological performance of fishes exposed to ocean acidification. Most of the up‐regulated genes at seeps were functionally involved in the maintenance of pH homeostasis and increased metabolism, and presented a deviation from neutral evolution expectations in their patterns of DNA polymorphisms, providing evidence for adaptive selection to ocean acidification. The targets of this adaptive selection are likely regulatory sequences responsible for the increased expression of these genes which would allow a fine‐tuned physiological regulation to maintain homeostasis and thrive at CO2 seeps. Our findings reveal that standing genetic variation in DNA sequences regulating the expression of genes in response to a reduced pH environment could provide for adaptive potential to near‐future ocean acidification in fishes. Moreover, with this study we provide a forthright methodology combining transcriptomics and genomics which can be applied to infer the adaptive potential to different environmental conditions in wild marine populations.

Continue reading ‘Natural CO2 seeps reveal adaptive potential to ocean acidification in fish’

Microalgal photosynthesis induces alkalization of aquatic environment as a result of H+ uptake independently from CO2 concentration – new perspectives for environmental applications


  • Microalgae photosynthesis induces strongly H+ uptake reversing ocean acidification.
  • Water alkalization through algal H+ uptake is independent from CO2 concentration.
  • New management approaches for reversing ocean acidification using algal H+ uptake.
  • Algal H+ uptake depends on essential nutrients, cell density and light intensity.
  • Acidification of aquatic environment induces microalgal photosynthesis and growth.


The photosynthetic process in microalgae and the extracellular proton environment interact with each other. The photosynthetic process in microalgae induces a pH increase in the aquatic environment as a result of cellular protons uptake rather than as an effect of CO2 consumption. The photosynthetic water photolysis and the reduction/oxidation cycle of the plastoquinone pool provide lumen with protons. Weak bases act as “permeant buffers” in lumen during the photosynthetic procedure, converting the ΔpH to Δψ. This is possibly the main reason for continuous light-driven proton uptake from the aquatic environment through cytosol and stroma, into the lumen. The proton uptake rate and, therefore, the microalgal growth is proportional to the light intensity, cell concentration, and extracellular proton concentration. The low pH in microalgae cultures, without limitation factors related to light and nutrients, strongly induces photosynthesis (and proton uptake) and, consequently, growth. In contrast, the mitochondrial respiratory process, in the absence of photosynthetic activity, does not substantially alter the culture pH. Only after intensification of the respiratory process, using exogenous glucose supply leads to significantly reduced pH values in the culture medium, almost exclusively through proton output. Enhanced dissolution of atmospheric CO2 in water causes the phenomenon of ocean acidification, which prevents the process of calcification, a significant process for numerous phytoplankton and zooplankton organisms, as well for corals. The proposed interaction between microalgal photosynthetic activity and proton concentration in the aquatic environment, independently from the CO2 concentration, paves the way for new innovative management strategies for reversing the ocean acidification.

Continue reading ‘Microalgal photosynthesis induces alkalization of aquatic environment as a result of H+ uptake independently from CO2 concentration – new perspectives for environmental applications’

Evaluation of the effect of local water chemistry on trace metal accumulation in Puget Sound shellfish shows that concentration varies with species, size, and location

Global climate change is causing ocean acidification (OA), warming, and decreased dissolved oxygen (DO) in coastal areas, which can cause physiological stress and compromise the health of marine organisms. While there is increased focus on how these stressors will affect marine species, there is little known regarding how changes in water chemistry will impact the bioaccumulation of trace metals. This study compared trace metal concentrations in tissue of Mediterranean mussels (Mytilus galloprovincialis) and Olympia oysters (Ostrea lurida) in Puget Sound, Washington, a region that experiences naturally low pH, seasonal hypoxia, and is surrounded by urbanized and industrialized areas. Shellfish were held at three sites (Carr Inlet, Point Wells, and Dabob Bay) where oceanographic data was continuously collected using mooring buoys. Using inductively coupled plasma mass-spectrometry (ICP-MS) to measure trace metals in the tissue, we found differences in accumulation of trace metals based on species, location, and shellfish size. Our study found differences between sites in both the mean metal concentrations and variability around the mean of those concentrations in bivalves. However, high metal concentrations in bivalves were not associated with high concentrations of metals in seawater. Metal concentrations in shellfish were associated with size: smaller shellfish had higher concentrations of metals. Carr Inlet at 20 m depth had the smallest shellfish and the highest metal concentrations. While we could not eliminate possible confounding factors, we also found higher metal concentrations in shellfish associated with lower pH, lower temperature, and lower dissolved oxygen (conditions seen at Carr Inlet at 20 m and to a lesser extent at Point Wells at 5 m depth). There were also significant differences in accumulation of metals between oysters and mussels, most notably copper and zinc, which were found in higher concentrations in oysters. These findings increase our understanding of spatial differences in trace metal bioaccumulation in shellfish from Puget Sound. Our results can help inform the Puget Sound aquaculture industry how shellfish may be impacted at different sites as climate change progresses and coastal pollution increases.

Continue reading ‘Evaluation of the effect of local water chemistry on trace metal accumulation in Puget Sound shellfish shows that concentration varies with species, size, and location’

Potential of maritime transport for ocean liming and atmospheric CO2 removal

Proposals to increase ocean alkalinity may make an important contribution to meeting climate change net emission targets, while also helping to ameliorate the effects of ocean acidification. However, the practical feasibility of spreading large amounts of alkaline materials in the seawater is poorly understood. In this study, the potential of discharging calcium hydroxide (slaked lime, SL) using existing maritime transport is evaluated, at the global scale and for the Mediterranean Sea. The potential discharge of SL from existing vessels depends on many factors, mainly their number and load capacity, the distance traveled along the route, the frequency of reloading, and the discharge rate. The latter may be constrained by the localized pH increase in the wake of the ship, which could be detrimental for marine ecosystems. Based on maritime traffic data from the International Maritime Organization for bulk carriers and container ships, and assuming low discharge rates and 15% of the deadweight capacity dedicated for SL transport, the maximum SL potential discharge from all active vessels worldwide is estimated to be between 1.7 and 4.0 Gt/year. For the Mediterranean Sea, based on detailed maritime traffic data, a potential discharge of about 186 Mt/year is estimated. The discharge using a fleet of 1,000 new dedicated ships has also been discussed, with a potential distribution of 1.3 Gt/year. Using average literature values of CO2 removal per unit of SL added to the sea, the global potential of CO2 removal from SL discharge by existing or new ships is estimated at several Gt/year, depending on the discharge rate. Since the potential impacts of SL discharge on the marine environment in the ships’ wake limits the rate at which SL can be applied, an overview of methodologies for the assessment of SL concentration in the wake of the ships is presented. A first assessment performed with a three-dimensional non-reactive and a one-dimensional reactive fluid dynamic model simulating the shrinking of particle radii, shows that low discharge rates of a SL slurry lead to pH variations of about 1 unit for a duration of just a few minutes.

Continue reading ‘Potential of maritime transport for ocean liming and atmospheric CO2 removal’

Testing for ocean acidification during the early Toarcian using δ44/40Ca and δ88/86Sr

During the early Toarcian, volcanic gases released by the Karoo-Ferrar large igneous province are widely believed to have caused severe environmental disturbances, including ocean acidification. Here we show records of δ44/40Ca and δ88/86Sr through the early Toarcian, as recorded in three groups of biogenic calcite: Megateuthididae belemnites, Passaloteuthididae belemnites, and brachiopods of the species Soaresirhynchia bouchardi. We evaluate the data to eliminate the influence on isotopic composition of varying temperature, calcification rate, and salinity, through the section that may mask the environmental signals.

Neither δ44/40Ca and δ88/86Sr show negative isotope excursions across the suggested acidification interval as would be expected had acidification occurred. A profile of δ11B, re-interpreted from a published study, shows no variation through the interval. Taken together, these data provide little support for ocean acidification at this time.

Values of δ88/86Sr are independent of temperature or Sr/Ca in our belemnites. For brachiopods, too few data are available to determine whether such a dependence exists. Values of δ44/40Ca show a weak temperature control of magnitude +0.020± 0.004‰/°C (2 s.d.). In belemnites, δ44/40Ca also correlates positively with Mg/Ca and Sr/Ca.

Continue reading ‘Testing for ocean acidification during the early Toarcian using δ44/40Ca and δ88/86Sr’

Extensive remineralization of peatland-derived dissolved organic carbon and acidification in the Sunda Shelf Sea, Southeast Asia

Southeast Asia is a hotspot of riverine export of terrigenous organic carbon to the ocean, accounting for ~10% of the global land-to-ocean riverine flux of terrigenous dissolved organic carbon (tDOC). While anthropogenic disturbance is thought to have increased the tDOC loss from peatlands in Southeast Asia, the fate of this tDOC in the marine environment and the potential impacts of its remineralization on coastal ecosystems remain poorly understood. We collected a multi-year biogeochemical time series in the central Sunda Shelf (Singapore Strait), where the seasonal reversal of ocean currents delivers water masses from the South China Sea first before (during Northeast Monsoon) and then after (during Southwest Monsoon) they have mixed with run-off from peatlands on Sumatra. The concentration and stable isotope composition of dissolved organic carbon, and colored dissolved organic matter spectra, reveal a large input of tDOC to our site during Southwest Monsoon. Using isotope mass balance calculations, we show that 60–70% of the original tDOC input is remineralized in the coastal waters of the Sunda Shelf, causing seasonal acidification by up to 0.10 pH units. The persistent CO2 oversaturation drives a CO2 efflux of 4.1 – 8.2 mol C m-2 yr-1 from the Singapore Strait, suggesting that a large proportion of the remineralized peatland tDOC is ultimately emitted to the atmosphere. However, incubation experiments show that the remaining 30–40% tDOC exhibits surprisingly low lability to microbial and photochemical degradation, suggesting that up to 20–30% of peatland tDOC might be relatively refractory and exported to the open ocean.

Continue reading ‘Extensive remineralization of peatland-derived dissolved organic carbon and acidification in the Sunda Shelf Sea, Southeast Asia’

Change of coral carbon isotopic response to anthropogenic Suess effect since around 2000s


  • The declining trend in the coral δ13C time series slowed or reversed after 2000.
  • The change of the declining rate in coral δ13C is not due to seawater chemistry.
  • The response of coral δ13C to Suess effect has changed since around 2000s.
  • The change results from coral acclimatization to external environmental stressors.


The stable carbon isotope composition (δ13C) in coral skeletons can be used to reconstruct the evolution of the dissolved inorganic carbon (DIC) in surface seawater, and its long-term declining trend during the past 200 years (∼1800-2000) reflects the effect of anthropogenic Suess effect on carbonate chemistry in surface oceans. The global atmospheric CO2 concentration still has been increasing since 2000, and the Suess effect is intensifying. Considering the coral’s ability of resilience and acclimatization to external environmental stressors, the response of coral δ13C to Suess effect may change and needs to be re-evaluated. In this study, ten long coral δ13C time series synthesized from different oceans were used to re-evaluate the response of coral carbonate chemistry to Suess effect under the changing environments. These δ13C time series showed a long-term declining trend since 1960s, but the declining rates slowed in eight time series since around 2000s. Considering that the declining rates of the DIC-δ13C in surface seawater from the Hawaii Ocean Time-series Station and Bermuda Atlantic Time-series Station has not changed since 2000 compared with those during 1960-1999, the change in the coral δ13C trends at eight of ten locations may indicate that the response of coral δ13C to the anthropogenic Suess effect has changed since around 2000s. This change may have resulted from coral acclimatization to external environmental stressors. To adapt to acidifying oceans, coral may have the ability to regulate the source of DIC in extracellular calcifying fluid and/or the utilization way of DIC, therefore the response of coral δ13C to anthropogenic Suess effect will change accordingly.

Continue reading ‘Change of coral carbon isotopic response to anthropogenic Suess effect since around 2000s’

Technical note: excess alkalinity in carbonate system reference materials

Certified reference materials (CRMs) for oceanic carbonate system measurements are critical for verifying the accuracy of laboratory protocols and the reliability of field sensors. CRMs are certified for total alkalinity and dissolved inorganic carbon, parameters that are (1) stable for a long period of time when a sample is properly stored and (2) not affected by changes in temperature and pressure. In experimentation initially designed to measure the total boron to salinity ratio of seawater, an interesting result has emerged regarding CRMs. A unique acidimetric titration method has indicated that three different batches of CRM contain excess alkalinity (i.e., alkalinity that is not attributable to inorganic bases included in the traditional definition of seawater total alkalinity) that is statistically greater than the excess alkalinity measured in open-ocean water from the Gulf of Mexico. Further, the amount of excess alkalinity appears to differ in certain CRM batches. Excess alkalinity in CRMs is likely caused by organic proton acceptors that are not completely oxidized by the ultraviolet sterilization procedure that CRMs undergo. The primary use of CRMs — to maintain the accuracy and consistency of carbonate system measurements — may be inhibited by excess alkalinity, which can cause differences in total alkalinity values determined by different titration methods. Excess alkalinity also invalidates the assumptions applied to CO2 system calculations, and so would produce incorrect values of CO2 system parameters calculated from certified total alkalinity and dissolved inorganic carbon values of CRMs. Finally, excess alkalinity analyses highlight the urgent need for the marine chemistry community to establish a universally agreed upon total boron to salinity ratio.

Continue reading ‘Technical note: excess alkalinity in carbonate system reference materials’

Seasonal marine carbon system processes in an Arctic coastal landfast sea ice environment observed with an innovative underwater sensor platform

Studying carbon dioxide in the ocean helps to understand how the ocean will be impacted by climate change and respond to increasing fossil fuel emissions. The marine carbonate system is not well characterized in the Arctic, where challenging logistics and extreme conditions limit observations of atmospheric CO2 flux and ocean acidification. Here, we present a high-resolution marine carbon system data set covering the complete cycle of sea-ice growth and melt in an Arctic estuary (Nunavut, Canada). This data set was collected through three consecutive yearlong deployments of sensors for pH and partial pressure of CO2 in seawater (pCO2sw) on a cabled underwater observatory. The sensors were remarkably stable compared to discrete samples: While corrections for offsets were required in some instances, we did not observe significant drift over the deployment periods. Our observations revealed a strong seasonality in this marine carbon system. Prior to sea-ice formation, air–sea gas exchange and respiration were the dominant processes, leading to increasing pCO2sw and reduced aragonite saturation state (ΩAr). During sea-ice growth, water column respiration and brine rejection (possibly enriched in dissolved inorganic carbon, relative to alkalinity, due to ikaite precipitation in sea ice) drove pCO2sw to supersaturation and lowered ΩAr to < 1. Shortly after polar sunrise, the ecosystem became net autotrophic, returning pCO2sw to undersaturation. The biological community responsible for this early switch to autotrophy (well before ice algae or phytoplankton blooms) requires further investigation. After sea-ice melt initiated, an under-ice phytoplankton bloom strongly reduced aqueous carbon (chlorophyll-a max of 2.4 µg L–1), returning ΩAr to > 1 after 4.5 months of undersaturation. Based on simple extrapolations of anthropogenic carbon inventories, we suspect that this seasonal undersaturation would not have occurred naturally. At ice breakup, the sensor platform recorded low pCO2sw (230 µatm), suggesting a strong CO2 sink during the open water season.

Continue reading ‘Seasonal marine carbon system processes in an Arctic coastal landfast sea ice environment observed with an innovative underwater sensor platform’

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Ocean acidification in the IPCC AR5 WG II

OUP book