Low pH Seawater Research Articles

Preliminary investigation on the potential involvement of an ABC-like gene in Halomicronema metazoicum (Cyanobacteria) tolerance to low seawater pH in an ocean acidification scenario

Decreasing ocean surface pH, called ocean acidification (OA), is among the major risks for marine ecosystems due to human-driven atmospheric pCO2 increase. Understanding the molecular mechanisms of adaptation enabling marine species to tolerate a lowered seawater pH could support predictions of consequences of future OA scenarios for marine life. This study examined whether the ATP-binding cassette (ABC)-like gene slr2019 confers tolerance to the marine cyanobacterium Halomicronema metazoicum to low seawater pH conditions (7.7, 7.2, 6.5) in short- and long-term exposures (7 and 30 d). Photosynthetic pigment content indicated that the species can tolerate all three lowered-pH conditions. At day 7, slr2019 was up-regulated at pH 7.7 while no changes were observed at lower pH. After 30-d exposure, a significant decrease in slr2019 transcript levels was observed in all low-pH treatments. These first results indicate an effect of low pH on the examined transporter expression in H. metazoicum.

Characterization of a novel antioxidant byssal protein from Mytilus coruscus foot

Mussel byssal proteins are of biomimetic importance for the development of novel underwater bio-adhesive agents. It is important to maintain a reduced state during the process of byssus adhesion. There are 19 mussel foot proteins (MFPs) have been reported in previous studies, among which only MFP-6 had been confirmed as an antioxidant protein in mussel byssus due to the function of cysteines, and playing an essential role in the redox balance of mussel byssus during adhesion process. Although the other four MFPs (MFP-16 ~ MFP-19) also have abundant cysteines, their function is still unknown. In this study, a novel mussel foot protein, named MFP-20, was identified from Mytilus coruscus foot. The sequential features, expression profile, and function of recombinant MFP-20 were verified. The results showed that MFP-20 has more abundant cysteines than other MFPs, the relative expression of mfp-20 was upregulated in Fe3+ stress and low pH seawater. In addition, different adhesive substrates induced significant changes of expression level of mfp-20. Furthermore, rMFP-20 showed strong antioxidant capacity in the DPPH assay, and the abundant cysteines in its sequence may play vital roles in the antioxidation activity. Our findings revealed the possible function of MFP-20 with a totally different sequence from the reported MFP-6 and provided new clues for exploring the redox balance of mussel byssus during the adhesion process.

Effect of seawater temperature and pH on the sperm motility of the European eel.

The current climate change situation could bring critical effects for marine species, especially those already considered endangered. Although some species can adapt fast to the environmental changes, it is necessary to get into the worst scenario and develop tools to anticipatedly assess the physiological effects of such environmental change. With this purpose, our study aims to determine the effect of a range of seawater temperatures and pHs on sperm motility in the European eel (Anguilla anguilla). Low seawater pH (6.5-7.4) decreased the eel sperm motility in comparison to the control (pH = 8.2). We also studied the combined effect of the pH of the artificial seminal plasma (the plasma where the sperm cells are suspended) with the pH of Artificial Sea Water (ASW, pH 7.8 or and 8.2). We did not find statistical differences in sperm motility and kinetic parameters caused by the artificial seminal plasma pH. However, seawater pH induced significantly higher values of total sperm motility, and the percentage of fast spermatozoa with a pH of 8.2 in comparison with a pH of 7.8. In contrast, the seawater temperature did not affect sperm motility parameters or sperm longevity. To study the effect of the interaction between seawater temperature and pH on sperm motility, two temperatures: 4 and 24°C, and two pHs 7.8 and 8.2, were tested. There were significant differences between temperature and pH in several kinetic parameters and, in general, the lowest values were observed in the samples activated at low temperature and low pH (4°C, pH 7.8). This work suggest that eel sperm motility and kinetics will not be affected by the expected changes in pH or temperature due to the climate change.

Porites' coral calcifying fluid chemistry regulation under normal- and low-pH seawater conditions in Palau Archipelago: Impacts on growth properties

Ongoing ocean acidification is known to be a major threat to tropical coral reefs. To date, only few studies have evaluated the impacts of natural long-term exposure to low-pH seawater on the chemical regulation and growth of reef-building corals. This work investigated the different responses of the massive Porites coral living at normal (pHsw ~ 8.03) and naturally low-pH (pHsw ~ 7.85) seawater conditions at Palau over the last decades. Our results show that both Porites colonies maintained similar carbonate properties (pHcf, [CO32−]cf, DICcf, and Ωcf) within their calcifying fluid since 1972. However, the Porites skeleton of the more acidified conditions revealed a significantly lower density (~ 1.21 ± 0.09 g·cm−3) than the skeleton from the open-ocean site (~ 1.41 ± 0.07 g·cm−3). Overall, both Porites colonies exerted a strong biological control to maintain stable calcifying fluid carbonate chemistry that favored the calcification process, especially under low-pH conditions. However, the decline in skeletal density observed at low pH provides critical insights into Porites vulnerability to future global change.

Effects of ocean acidification on growth and photophysiology of two tropical reef macroalgae.

Macroalgae can modify coral reef community structure and ecosystem function through a variety of mechanisms, including mediation of biogeochemistry through photosynthesis and the associated production of dissolved organic carbon (DOC). Ocean acidification has the potential to fuel macroalgal growth and photosynthesis and alter DOC production, but responses across taxa and regions are widely varied and difficult to predict. Focusing on algal taxa from two different functional groups on Caribbean coral reefs, we exposed fleshy (Dictyota spp.) and calcifying (Halimeda tuna) macroalgae to ambient and low seawater pH for 25 days in an outdoor experimental system in the Florida Keys. We quantified algal growth, calcification, photophysiology, and DOC production across pH treatments. We observed no significant differences in the growth or photophysiology of either species between treatments, except for lower chlorophyll b concentrations in Dictyota spp. in response to low pH. We were unable to quantify changes in DOC production. The tolerance of Dictyota and Halimeda to near-future seawater carbonate chemistry and stability of photophysiology, suggests that acidification alone is unlikely to change biogeochemical processes associated with algal photosynthesis in these species. Additional research is needed to fully understand how taxa from these functional groups sourced from a wide range of environmental conditions regulate photosynthesis (via carbon uptake strategies) and how this impacts their DOC production. Understanding these species-specific responses to future acidification will allow us to more accurately model and predict the indirect impacts of macroalgae on coral health and reef ecosystem processes.

Interactive effects of ocean acidification and water flow on growth and recruitment of early successional coralline algal communities

ABSTRACTCoralline algae play crucial roles in near-shore ecosystems but are susceptible to ocean acidification (OA). It has been hypothesized that low water velocity, allowing localized photosynthesis-driven pH-increases in the coralline surface boundary layer, could buffer against the negative impacts of OA. To test how water motion affected the sensitivity of coralline algae to OA, coralline communities (from 2 m and 10 m depth) were grown for 220 days at two pH levels (present-day: pH 8.03, OA: pH 7.65) under differing inflow rates (400, 200 and 100 ml min–1) providing water velocities of 2.7, 5.9 and 7.8 cm s–1. Communities from both depths were grown together, photographed to assess growth, and the resulting recruitment was evaluated at the experiment’s conclusion. Low seawater pH reduced growth by c. 11% (highest flow), further decreased by >23% under the lowest flow. This reduction resulted in differential outcomes for the two depths, with skeletal net-dissolution under the combination of low flow and pH 7.65 for 10 m communities. Furthermore, there was a synergistic interaction between the effects of flow and pH, whereby the negative effect of OA strengthened under low flow, with recruitment halved at pH 7.65. This demonstrates that OA impacts can be modulated by the flow environment. Surprisingly, increased flow rates/water velocities reduced negative impacts of low pH, thus further challenging the notion that slow flow habitats offer protection from OA. The observed interactions between water flow and OA on early successional communities and their recruits may hold implications for the future of rocky reef systems dominated by these communities.

Ocean acidification causes fundamental changes in the cellular metabolism of the Arctic copepod Calanus glacialis as detected by metabolomic analysis

Using a targeted metabolomic approach we investigated the effects of low seawater pH on energy metabolism in two late copepodite stages (CIV and CV) of the keystone Arctic copepod species Calanus glacialis. Exposure to decreasing seawater pH (from 8.0 to 7.0) caused increased ATP, ADP and NAD+ and decreased AMP concentrations in stage CIV, and increased ATP and phospho-L-arginine and decreased AMP concentrations in stage CV. Metabolic pathway enrichment analysis showed enrichment of the TCA cycle and a range of amino acid metabolic pathways in both stages. Concentrations of lactate, malate, fumarate and alpha-ketoglutarate (all involved in the TCA cycle) increased in stage CIV, whereas only alpha-ketoglutarate increased in stage CV. Based on the pattern of concentration changes in glucose, pyruvate, TCA cycle metabolites, and free amino acids, we hypothesise that ocean acidification will lead to a shift in energy production from carbohydrate metabolism in the glycolysis toward amino acid metabolism in the TCA cycle and oxidative phosphorylation in stage CIV. In stage CV, concentrations of most of the analysed free fatty acids increased, suggesting in particular that ocean acidification increases the metabolism of stored wax esters in this stage. Moreover, aminoacyl-tRNA biosynthesis was enriched in both stages indicating increased enzyme production to handle low pH stress.

Ocean acidification modifies behaviour of shelf seabed macrofauna: A laboratory study on two ecosystem engineers, Abra alba and Lanice conchilega

The feeding activity and burrow ventilation by benthic invertebrates importantly affect the biodiversity and functioning of seafloor sediments. Here we investigated how ocean acidification can modify these behavioural activities in two common and abundant macrofaunal ecosystem engineering species in temperate continental shelf communities: the white furrow shell Abra alba and the sand mason Lanice conchilega. Using time-lapse imagery and sediment porewater hydraulic signatures we show that both species adapt their behaviour in response to predicted future pH conditions (−0.3 units). During a three-week laboratory experiment, A. alba reduced the duration per feeding event when suspension and deposit feeding (by 86 and 53%, respectively), and almost completely ceased suspension feeding under reduced seawater pH in comparison to ambient seawater pH (pH ∼ 8.2). This behavioural change reduces the intake of low pH water during feeding and respiration. L. conchilega increased its piston-pumping frequency by 30 and 52%, respectively, after one and two weeks of exposure to future pH conditions (−0.3 units) relative to ambient conditions. This change in irrigation activity suggests higher metabolic demands under low seawater pH, and also extended low water column pH conditions deeper into the seafloor. Because the distribution of other populations depends on the physicochemical setting by our focal species, we argue that the demonstrated behavioural plasticity will likely have cascading effects on seafloor diversity and functioning, highlighting the complexity of how ocean acidification, and climate change in general, will affect seafloor ecology.

Molecular basis of ocean acidification sensitivity and adaptation in Mytilus galloprovincialis

SummaryPredicting the potential for species adaption to climate change is challenged by the need to identify the physiological mechanisms that underpin species vulnerability. Here, we investigated the sensitivity to ocean acidification in marine mussels during early development, and specifically the trochophore stage. Using RNA and DNA sequencing and in situ RNA hybridization, we identified developmental processes associated with abnormal development and rapid adaptation to low pH. Trochophores exposed to low pH seawater exhibited 43 differentially expressed genes. Gene annotation and in situ hybridization of differentially expressed genes point to pH sensitivity of (1) shell field development and (2) cellular stress response. Five genes within these two processes exhibited shifts in allele frequencies indicative of a potential for rapid adaptation. This case study contributes direct evidence that protecting species’ existing genetic diversity is a critical management action to facilitate species resilience to climate change.

The spatial distribution of surface ocean primary productivity in the wake of Marinoan global glaciation

Termination of the Marinoan global glaciation (~650–635 Ma) was followed by the diversification of eukaryotes (e.g., early animals) and oxygenation of deep oceans in the early Ediacaran Period. Previous studies indicate the recovery of marine primary productivity immediately before the cap carbonate precipitation but after melting of the Marinoan global glaciation. Pyrite concretions from the topmost Nantuo Formation in the Yangtze Block, South China, decrease in abundance from shelf to basin facies, while their high positive sulfur (S) isotope values argue the development of oceanic euxinia, which require ample supply of organic matter, presumably reflecting the recovery of marine productivity. However, pyrite contents and pyrite S isotopes alone cannot uniquely constrain the extent and spatial distribution of surface ocean organic matter production. In this study, we conducted in situ analyses of pyrite iron (Fe) (δ56Fepy) and S isotopes (δ34Spy) of pyrite concretions collected from four sections of the Nantuo Formation, spanning from shelf to basin environments. Pyrite from different facies has distinct δ34Spy and δ56Fepy values. In general, δ34Spy values display an increasing trend from shelf to basin, whereas δ56Fepy values demonstrate an opposite trend with the lowest value in the basin sections. The opposite δ34Spy and δ56Fepy shelf-basin gradients strongly argue against the hydrothermal origin, yet verify the diagenetic precipitation of Nantuo pyrite in sediment porewater. Numerical models were developed to quantify the microbial sulfate reduction (MSR), microbial iron reduction (MIR) and pyrite precipitation processes. The modeling results provide an explanation for the shelf-basin decrease of δ56Fepy values, indicating that both the fraction of MIR (fMIR) and the fraction of Fe2+ consumed by pyrite precipitation (fpy) increase from shelf to basin sections. In addition, high δ34Spy values and pyrite contents in the basin sections also imply more intense MSR and higher supplies of H2S from sulfidic seawater. Both MSR and MIR were fueled by organic matter, thus suggesting that the surface ocean primary productivity displayed an unusual increasing trend toward the open ocean, which was different from the higher productivity in modern near-shore regions. We speculate that the reversed shelf-basin gradient of surface ocean primary productivity might be attributed to high P concentration in the post-glacial ocean. Terrestrial riverine P supply, on the contrary, might have diluted seawater P concentration in the near-shore regions. Therefore, our result indicates that the recovery of marine productivity in the aftermath of the Marinoan global glaciation may be not controlled by the availability of nutrients, instead, the immediate recovery of productivity might have been prohibited by, e.g., low seawater pH at a high atmospheric pCO2 level in the initial melting of the Marinoan global glaciation. The marine primary productivity did not recover until a substantive rise of seawater pH, during which deglacial intense continental weathering delivered abundant P into the ocean and accordingly elevated the seawater P concentration.

PH variability at volcanic CO2 seeps regulates coral calcifying fluid chemistry.

Coral reefs are iconic ecosystems with immense ecological, economic and cultural value, but globally their carbonate-based skeletal construction is threatened by ocean acidification (OA). Identifying coral species that have specialised mechanisms to maintain high rates of calcification in the face of declining seawater pH is of paramount importance in predicting future species composition, and growth of coral reefs. Here, we studied multiple coral species from two distinct volcanic CO2 seeps in Papua New Guinea to assess their capacity to control their calcifying fluid (CF) chemistry. Several coral species living under conditions of low mean seawater pH, but with either low or high variability in seawater pH, were examined and compared with those living in 'normal' (non-seep) ambient seawater pH. We show that when mean seawater pH is low but highly variable, corals have a greater ability to maintain constant pHcf in their CF, but this characteristic was not linked with changes in abundance. Within less variable low pH seawater, corals with limited reductions in pHcf at the seep sites compared with controls tended to be more abundant at the seep site than at the control site. However, this finding was strongly influenced by a single species (Montipora foliosa), which was able to maintain complete pHcf homeostasis. Overall, although our findings indicate that there might be an association between ecological success and greater pHcf homeostasis, further research with additional species and at more sites with differing seawater pH regimes is required to solidify inferences regarding coral ecological success under future OA.

Active biogeochemical cycles during the Marinoan global glaciation

Termination of the Marinoan global glaciation (650–635 million years ago, Ma) was immediately followed by the diversification of eukaryotes and possible occurrence of animals, suggesting the potential linkage between biological evolution and global glaciation. It is proposed that the post-glacial eukaryote evolution might have been triggered by environmental stress imposed by the extreme pan-glacial condition. However, how life survived through the global glaciation remains speculative. Neither is known about the habitability when the ocean was completely or mostly frozen. In this study, we explore the marine carbon and sulfur biogeochemical cycles during the Nantuo (Marinoan) glaciation (650–635 Ma) in South China. Both organic carbon (δ13Corg) and pyrite sulfur isotopes (δ34Spy) show significant stratigraphic variations, suggesting active biogeochemical cycles in the pan-glacial condition. By coupling both δ13Corg and δ34Spy data, we develop numerical models to constrain marine productivity and redox conditions during the Nantuo glaciation. The marine primary productivity showed a sharp decline in the onset of glaciation and recovered right before the cap carbonate precipitation. An episodic recovery of primary productivity was observed in the non-glacial interval between the two glacial episodes. In contrast, the marine productivity was still suppressed in initial deglaciation, during which the continental weathering was intense, presumably indicating high atmospheric CO2 level and low seawater pH value. The final recovery of marine primary productivity occurred in the topmost of Nantuo Formation, when the weathering intensity was already low. Therefore, the active biogeochemical cycle implies a sustained habitability, warranting the survivorship in the pan-glacial ocean, while the persistently low and delayed recovery of marine productivity might have imposed environmental stress for tens of million years, paving the way for the evolution of animals.

Molecular mechanisms underlying responses of the Antarctic coral Malacobelemnon daytoni to ocean acidification

Benthic organisms of the Southern Ocean are particularly vulnerable to ocean acidification (OA), as they inhabit cold waters where calcite-aragonite saturation states are naturally low. OA most strongly affects animals with calcium carbonate skeletons or shells, such as corals and mollusks. We exposed the abundant cold-water coral Malacobelemnon daytoni from an Antarctic fjord to low pH seawater (LpH) (7.68 ± 0.17) to test its physiological responses to OA, at the level of gene expression (RT-PCR) and enzyme activity. Corals were exposed in short- (3 days) and long-term (54 days) experiments to two pCO2 conditions (ambient and elevated pCO2 equaling RCP 8.5, IPCC 2019, approximately 372.53 and 956.78 μatm, respectively).Of the eleven genes studied through RT-PCR, six were significantly upregulated compared with control in the short-term in the LpH condition, including the antioxidant enzyme superoxide dismutase (SOD), Heat Shock Protein 70 (HSP70), Toll-like receptor (TLR), galaxin and ferritin. After long-term exposure to low pH conditions, RT-PCR analysis showed seven genes were upregulated. These include the mannose-binding C-Lectin and HSP90. Also, the expression of TLR and galaxin, among others, continued to be upregulated after long-term exposure to LpH. Expression of carbonic anhydrase (CA), a key enzyme involved in calcification, was also significantly upregulated after long-term exposure. Our results indicated that, after two months, M. daytoni is not acclimatized to this experimental LpH condition. Gene expression profiles revealed molecular impacts that were not evident at the enzyme activity level. Consequently, understanding the molecular mechanisms behind the physiological processes in the response of a coral to LpH is critical to understanding the ability of polar species to cope with future environmental changes. Approaches integrating molecular tools into Antarctic ecological and/or conservation research make an essential contribution given the current ongoing OA processes.

Volcanic CO2 seep geochemistry and use in understanding ocean acidification

Ocean acidification is one of the most dramatic effects of the massive atmospheric release of anthropogenic carbon dioxide (CO2) that has occurred since the Industrial Revolution, although its effects on marine ecosystems are not well understood. Submarine volcanic hydrothermal fields have geochemical conditions that provide opportunities to characterise the effects of elevated levels of seawater CO2 on marine life in the field. Here, we review the geochemical aspects of shallow marine CO2-rich seeps worldwide, focusing on both gas composition and water chemistry. We then describe the geochemical effects of volcanic CO2 seepage on the overlying seawater column. We also present new geochemical data and the first synthesis of marine biological community changes from one of the best-studied marine CO2 seep sites in the world (off Vulcano Island, Sicily). In areas of intense bubbling, extremely high levels of pCO2 (> 10,000 μatm) result in low seawater pH (< 6) and undersaturation of aragonite and calcite in an area devoid of calcified organisms such as shelled molluscs and hard corals. Around 100–400 m away from the Vulcano seeps the geochemistry of the seawater becomes analogous to future ocean acidification conditions with dissolved carbon dioxide levels falling from 900 to 420 μatm as seawater pH rises from 7.6 to 8.0. Calcified species such as coralline algae and sea urchins fare increasingly well as sessile communities shift from domination by a few resilient species (such as uncalcified algae and polychaetes) to a diverse and complex community (including abundant calcified algae and sea urchins) as the seawater returns to ambient levels of CO2. Laboratory advances in our understanding of species sensitivity to high CO2 and low pH seawater, reveal how marine organisms react to simulated ocean acidification conditions (e.g., using energetic trade-offs for calcification, reproduction, growth and survival). Research at volcanic marine seeps, such as those off Vulcano, highlight consistent ecosystem responses to rising levels of seawater CO2, with the simplification of food webs, losses in functional diversity and reduced provisioning of goods and services for humans.

Risks of consuming cadmium-contaminated shellfish under seawater acidification scenario: Estimates of PBPK and benchmark dose.

We aim to assess the risks of renal dysfunction and osteoporosis that is attributed to the seawater acidification caused cadmium (Cd) level increase in human consumed shellfish. A physiology-based pharmacokinetic model was used to estimate Cd concentrations in urine and blood among shellfish-only consumers and among the general population. We used the benchmark dose (BMD) method to determine the threshold limits of Cd in urine for renal dysfunction and in blood for osteoporosis for assessing the human health risk. Our results revealed that seawater acidification could increase the Cd accumulation in shellfish by 10-13% compared to the situations under current pH levels. Under the lower seawater pH level, the daily intake of Cd could increase by 21%-67% among shellfish-only consumers, and by 13%-17% among the general population. Our findings indicated that seawater acidification would lead to a marginal increase in Cd intake among humans in shellfish-only consumers. The results of BMDs of urinary Cd showed that the threshold limits for renal dysfunction at 5% were 3.00μgg-1 in males and 12.35μgg-1 in females. For osteoporosis, the estimated BMDs of blood Cd were 7.95μgL-1 in males and 1.23μgL-1 in females. These results of the risk of Cd intake showed that the consumption of Cd-contaminated shellfish in the general population is largely unaffected by changes in seawater pH levels. Notably, the potential impact of seawater acidification on renal dysfunction for males in shellfish-only consumers face a 14% increase of risk.

Multigenerational Mitigating Effects of Ocean Acidification on In Vivo Endpoints, Antioxidant Defense, DNA Damage Response, and Epigenetic Modification in an Asexual Monogonont Rotifer.

Ocean acidification (OA) is caused by changes in ocean carbon chemistry due to increased atmospheric pCO2 and is predicted to have deleterious effects on marine ecosystems. While the potential impacts of OA on many marine species have been studied, the multigenerational effects on asexual organisms remain unknown. We found that low seawater pH induced oxidative stress and DNA damage, decreasing growth rates, fecundity, and lifespans in the parental generation, whereas deleterious effects on in vivo endpoints in F1 and F2 offspring were less evident. The findings suggest that multigenerational adaptive effects play a role in antioxidant abilities and other defense mechanisms. OA-induced DNA damage, including double-strand breaks (DSBs), was fully repaired in F1 offspring of parents exposed to OA for 7 days, indicating that an adaptation mechanism may be the major driving force behind multigenerational adaptive effects. Analysis of epigenetic modification in response to OA involved examination of histone modification of DNA repair genes and a chromatin immunoprecipitation assay, as Bombus koreanus has no methylation pattern for CpG in its genome. We conclude that DSBs, DNA repair, and histone modification play important roles in multigenerational plasticity in response to OA in an asexual monogonont rotifer.

Chemical archeoceanography

Elemental fluxes to the ocean are expected to increase with the surface area of continental exposure to weathering and atmospheric PCO2. The record of phosphorus in sediments, which has no notable source within the ocean, and the radiogenic strontium isotopes in Archean carbonates indicate that, prior to the Great Oxidation Event (GOE), subaerial expanses represented only about 20% of the modern continental surface area, i.e. 7% of the surface of the Earth. Because these simple first-order observations, in contrast to the low oxygen content of the pre-GOE atmosphere, have so far received only little attention in the appraisal of the marine chemistry of the early Earth, a reassessment of the chemistry of the pre-GOE ocean is warranted. Here we discuss some of the geochemical cycles of the Archean world, including protons, alkalinity, electrons, and other electrolytes, and attempt to build a first conceptual framework for Chemical Archeoceanography. The smaller subaerial exposures characterizing the Archean and the low abundance of Archean carbonates and mudstones imply that the flux of alkalinity to the ocean was much weaker than today and therefore that the capacity of the runoff to neutralize the high-temperature hydrothermal fluids was less important. Such a reduced flux in turn entails lower seawater pH and higher chlorinity. The lack of atmospheric O2 allowed iron to be in its soluble Fe(II) form and to reduce HCO3− to CH4 while liberating large amounts of protons. The low pH of the pre-GOE ocean and the reduced alkalinity input, reinforced by scant P supply, account for reduced carbonate precipitation. Ocean chemistry evolved under the control of two changing factors: (i) the balance between chemical weathering and hydrothermal fluxes and (ii) the oxygen pressure in the ocean and the atmosphere. Seawater iron concentration was controlled by high [Fe2+]/[H+]2 ratios. With the temperature of hydrothermal fluids at mid-ocean ridges and other active volcanic edifices being determined by the expansion properties of seawater, the chemistry of hydrothermal fluids is controlled by the chlorinity of the ocean. Of all the major element cycles in seawater, those of Na, Mg, and P seem to be unbalanced when runoff falls below the modern value. The very low P content of banded iron formations is inconsistent with a major role of biological activity in the oxidation of Fe2+ dissolved in the Archean ocean. Prior to the GOE, banded iron formations were the major sedimentary sink of seawater cations, a role now played by carbonates. The controls of seawater alkalinity, which today are exerted by the Ca2+–CaCO3 couple, was exerted by dissolved Fe2+-magnetite or Fe2+-ferrihydrite. Plain language summaryWe here evaluate the constraints on seawater chemistry before free oxygen was introduced into the atmosphere some 2.4 billion years ago. We suggest a simple conceptual framework which we validated on modern seawater and which is based on two so-far largely overlooked observations, namely that the phosphorus concentration and strontium isotopic records in ancient sediments require that emerged continental land masses were covering only ~7% of Earth's surface at the time of the Great Oxidation Event instead of 30% today. Atmospheric and seawater chemistry critically depend on this proportion as well as on the chlorinity of the ocean. The oxygen-free atmosphere allowed iron to remain in solution and to reduce atmospheric carbon dioxide to methane. The pH of the ancient oceans must have been lower because less river water was available to neutralize the acidic submarine high-temperature hydrothermal fluids emitted at mid-ocean ridges. Limited continental surface starved the sedimentary column for clays. The low pH and scant phosphorus drainage led to rare carbonate deposition. We conclude by proposing a new scheme for Archean marine chemistry and geochemical cycles that can explain the chemical and geological observations from the Archean and early Proterozoic rock record.

Vertical distribution of echinoid larvae in pH stratified water columns

The abundance and distribution of many benthic marine organisms are shaped by the success of their dispersive larval life-history stage. An increasing number of studies have shown that ocean acidification negatively impacts the larval life-history stage, including those of echinoids which are commercially and ecologically important. However, little is known about the behavioral responses of echinoid larvae to different pH levels in the water column. Changes in vertical movement in response to the naturally occurring pH variations caused by biological activities and/or physical conditions could affect dispersal and recruitment. In this study, we quantified the vertical distribution of larval sand dollars, Dendraster excentricus (Echinodermata), in water columns with stratified layers of seawater varying in salinity and pH. When larval sand dollars swimming upwards in ambient seawater (pHNBS 7.86 ± 0.04) encountered a layer of low pH (pHNBS 7.54 ± 0.04) seawater, about half of the individuals (53 ± 28%) were aggregated near the transition layer 60 min after the start of the experiment. Preliminary video analysis showed larvae reversed their direction of travel and altered the shape of their helical swimming trajectories, upon encountering the transition layer moving from ambient to low pH water. In contrast, when larval sand dollars swimming upwards in acidified seawater encountered ambient seawater, they continued to swim upward to aggregate near the top of the column. In control water columns with uniform pH, larvae did not change swimming behavior regardless of whether pH was ambient or acidified and whether salinity was uniform or stratified. These results indicate that stratification itself did not strongly affect the vertical distributions of larvae. These observations suggest that echinoid larvae, and perhaps many other types of planktonic larvae, may use behavioral plasticity to reduce exposure to stresses from ocean acidification. The presence and effectiveness of these responses may improve the ability of larvae to cope with stressful, dynamic habitats, and hence may be significant to prediction of potential impacts of global climate change.

From greenhouse to icehouse: Nitrogen biogeochemistry of an epeiric sea in the context of the oxygenation of the Late Devonian atmosphere/ocean system

The Late Devonian emergence of extensive arborescent terrestrial ecosystems produced changes in the Earth's atmosphere and climate that resulted in substantial changes to the biogeochemistry of marine ecosystems. The biogeochemistry of nitrogen in epeiric seas was particularly susceptible to alteration because of its dependence upon the series of redox-mediated reactions that comprise the marine N cycle. In order to explore the impact of climate change on N biogeochemistry in a Late Devonian epeiric sea, we sampled a core from the Appalachian Basin that spans the interval from the greenhouse climate at the base of the Famennian period to glacial conditions near its conclusion. Based upon stable isotope analysis of N, C, and S as well as elemental analysis of N, C, P, S, and Fe, we contend that two distinct biogeochemical regimes obtained during the contrasting climates. The greenhouse regime featured low seawater O2 and pH that served to significantly curtail the oxidation of ammonia – i.e. nitrification – resulting in an ammonium-dominated water column and low sediment δ15N values. The greenhouse also featured more extensive recycling of C, N, and P. In contrast, the higher seawater O2 and pH of the icehouse regime permitted nitrification in the water column resulting in a nitrate-dominated system and higher sediment δ15N values. We conclude that nitrification was the key component of the N cycle that differentiated the two climate/biogeochemical regimes.

The effects of low seawater pH on energy storage and heat shock protein 70 expression in a bivalve Limecola balthica

Though biological consequences of CCS (Carbon Capture and Storage) implementation into the marine environment have received substantial research attention, the impact of potential CO2 leakage on benthic infauna in the Baltic Sea remained poorly recognized. This study quantified medium-term (56-day laboratory exposure) effects of CO2-induced seawater acidification (pH 7.7, 7.0 and 6.3) on energetic reserves and heat-shock protein HSP70 expression of adult bivalve Limecola balthica from the southern Baltic. While no clear impact was evident in the most acidic treatment (pH 6.3), moderate seawater hypercapnia (pH 7.0) induced elevated catabolism of high caloric reserves (carbohydrates including glycogen and lipids) in order to provide energy to cover enhanced metabolic requirements for acid-base regulation. Biochemical response did not involve, however, breakdown of proteins, suggesting that they were not utilized as metabolic substrates. As indicated also by subtle variations in the chaperone protein HSP70, the clams demonstrated high CO2 tolerance, presumably through development of efficient defensive/compensatory mechanisms during their larval and/or ontogenic life stages.