Geochemical survey of Levante Bay,Vulcano Island (Italy), a natural laboratory for the study of ocean acidification

Shallow submarine gas vents in Levante Bay, Vulcano Island (Italy), emit around 3.6t CO₂ per day providing a natural laboratory for the study of biogeochemical processes related to seabed CO₂ leaks and ocean acidification. The main physico-chemical parameters (T, pH and Eh) were measured at more than 70 stations with 40 seawater samples were collected for chemical analyses. The main gas vent area had high concentrations of dissolved hydrothermal gases, low pH and negative redox values all of which returned to normal seawater values at distances of about 400 m from the main vents. Much of the bay around the vents is corrosive to calcium carbonate; the north shore has a gradient in seawater carbonate chemistry that is well suited to studies of the effects of long-term increases in CO₂ levels. This shoreline lacks toxic compounds (such as H₂S) and has a gradient in carbonate saturation states.     

Linkage of deep sea rapid acidification process and extinction of benthic foraminifera in the deep sea at the Paleocene/Eocene transition

Ocean Drilling Program Leg 199 Site 1220 provides a continuous sedimentary section across the Paleocene/Eocene (P/E) transition in the carbonate‐bearing sediments on 56–57 Ma oceanic crust. The large negative δ¹³C shift in seawater is likely due to the disintegration of methane hydrate, which is expected to be rapidly changed to carbon dioxide in the atmosphere and well‐oxygenated seawater, leading to a reduction in deep‐sea pH. A pH decrease was very likely responsible for the emergence of agglutinated foraminiferal fauna as calcareous fauna was eliminated by acidification at the P/E transition at Site 1220. The absence of the more resistant calcareous benthic foraminifera and the presence of the planktonic foraminifera at Site 1220 is interesting and unique, which indicates that calcareous benthic foraminifera suffered greatly from living on the seafloor. Box model calculation demonstrates that, assuming the same mean alkalinity as today, pCO₂ must increase from 280 ppm to about 410 ppm for the calcite undersaturation in the deep ocean and for the oversaturation in the surface ocean during the P/E transition. The calculated increased pCO₂ coincides with paleo‐botanical evidence. The current global emission rate (～7.3 peta (10¹⁵) gC/y) of anthropogenic carbon input is approximately 30 times of the estimate at the P/E transition. The results at the P/E transition give an implication that the deep sea benthic fauna will be threatened in future in combination with ocean acidification, increased sea surface temperature and more stratified surface water.     

Consequences of a simulated rapid ocean acidification event for benthic ecosystem processes and functions

Whilst the biological consequences of long-term, gradual changes in acidity associated with the oceanic uptake of atmospheric carbon dioxide (CO₂) are increasingly studied, the potential effects of rapid acidification associated with a failure of sub-seabed carbon storage infrastructure have received less attention. This study investigates the effects of severe short-term (8 days) exposure to acidified seawater on infaunal mediation of ecosystem processes (bioirrigation and sediment particle redistribution) and functioning (nutrient concentrations). Following acidification, individuals of Amphiura filiformis exhibited emergent behaviour typical of a stress response, which resulted in altered bioturbation, but limited changes in nutrient cycling. Under acidified conditions, A. filiformis moved to shallower depths within the sediment and the variability in occupancy depth reduced considerably. This study indicated that rapid acidification events may not be lethal to benthic invertebrates, but may result in behavioural changes that could have longer-term implications for species survival, ecosystem structure and functioning.     

Effects of elevated pCO2 on reproductive properties of the benthic copepod Tigriopus japonicus and gastropod Babylonia japonica

We investigated the effects of elevated pCO₂ in seawater both on the acute mortality and the reproductive properties of the benthic copepod Tigriopus japonicus and gastropod Babylonia japonica with the purpose of accumulating basic data for assessing potential environmental impacts of sub-sea geological storage of anthropogenic CO₂ in Japan. Acute tests showed that nauplii of T. japonicus have a high tolerance to elevated pCO₂ environments. Full life cycle tests on T. japonicus indicated NOEC = 5800 μatm and LOEC = 37,000 μatm. Adult B. japonica showed remarkable resistance to elevated pCO₂ in the acute tests. Embryonic development of B. japonica showed a NOEC = 1500 μatm and LOEC = 5400 μatm. T. japonicus showed high resistance to elevated pCO₂ throughout the life cycle and B. japonica are rather sensitive during the veliger stage when they started to form their shells.     

Impact of elevated levels of CO2 on animal mediated ecosystem function: The modification of sediment nutrient fluxes by burrowing urchins

A mesocosm experiment was conducted to quantify the relationships between the presence and body size of two burrowing heart urchins (Brissopsis lyrifera and Echinocardium cordatum) and rates of sediment nutrient flux. Furthermore, the impact of seawater acidification on these relationships was determined during this 40-day exposure experiment. Using carbon dioxide (CO₂) gas, seawater was acidified to pH_NBS 7.6, 7.2 or 6.8. Control treatments were maintained in natural seawater (pH ≈ 8.0). Under normocapnic conditions, burrowing urchins were seen to reduce the sediment uptake of nitrite or nitrate whilst enhancing the release of silicate and phosphate. In acidified (hypercapnic) treatments, the biological control of biogeochemical cycles by urchins was significantly affected, probably through the combined impacts of high CO₂ on nitrifying bacteria, benthic algae and urchin behaviour. This study highlights the importance of considering biological interactions when predicting the consequences of seawater acidification on ecosystem function.     

Carbon isotopic compositions of Recent planktonic foraminifera of the Indian Ocean

Carbon and oxygen isotopic determinations have been made of 29 species of Recent Indian Ocean planktonic foraminifera. Fourteen core-top samples were used and as many as 18 species were chosen from a single core-top sample. The δ¹³C of the foraminifera was compared with that of total dissolved CO₂ (ΣCO₂) and of calcite precipitated in isotopic equilibrium with ΣCO₂. The foraminiferal calcite is always at least 1.2‰ less than the value estimated for equilibrium calcite. This carbon isotopic disequilibrium suggests the partial utilization of¹³C-depleted metabolic CO₂. The calcite tests of several species, however, have δ¹³C values which are similar to the δ¹³C of ΣCO₂ in seawater. This relationship suggests that important paleohydrographic information may be obtained from carbon isotope records based on analyses of several foraminiferal species from single deep-sea sediment samples.     

Potential acidification impacts on zooplankton in CCS leakage scenarios

Carbon capture and storage (CCS) technologies involve localized acidification of significant volumes of seawater, inhabited mainly by planktonic species. Knowledge on potential impacts of these techniques on the survival and physiology of zooplankton, and subsequent consequences for ecosystem health in targeted areas, is scarce. The recent literature has a focus on anthropogenic greenhouse gas emissions into the atmosphere, leading to enhanced absorption of CO₂ by the oceans and a lowered seawater pH, termed ocean acidification. These studies explore the effects of changes in seawater chemistry, as predicted by climate models for the end of this century, on marine biota. Early studies have used unrealistically severe CO₂/pH values in this context, but are relevant for CCS leakage scenarios. Little studied meso- and bathypelagic species of the deep sea may be especially vulnerable, as well as vertically migrating zooplankton, which require significant residence times at great depths as part of their life cycle.     

Distribution of sea urchins living near shallow water CO2 vents is dependent upon species acid–base and ion-regulatory abilities

To reduce the negative effect of climate change on Biodiversity, the use of geological CO₂ sequestration has been proposed; however leakage from underwater storages may represent a risk to marine life. As extracellular homeostasis is important in determining species’ ability to cope with elevated CO₂, we investigated the acid–base and ion regulatory responses, as well as the density, of sea urchins living around CO₂ vents at Vulcano, Italy. We conducted in situ transplantation and field-based laboratory exposures to different pCO₂/pH regimes. Our results confirm that sea urchins have some ability to regulate their extracellular fluid under elevated pCO₂. Furthermore, we show that even in closely-related taxa divergent physiological capabilities underlie differences in taxa distribution around the CO₂ vent. It is concluded that species distribution under the sort of elevated CO₂ conditions occurring with leakages from geological storages and future ocean acidification scenarios, may partly be determined by quite subtle physiological differentiation.     

Effects of elevated CO2 on the reproduction of two calanoid copepods

Some planktonic groups suffer negative effects from ocean acidification (OA), although copepods might be less sensitive. We investigated the effect of predicted CO₂ levels (range 480–750 ppm), on egg production and hatching success of two copepod species, Centropages typicus and Temora longicornis. In these short-term incubations there was no significant effect of high CO₂ on these parameters. Additionally a very high CO₂ treatment, (CO₂ = 9830 ppm), representative of carbon capture and storage scenarios, resulted in a reduction of egg production rate and hatching success of C. typicus, but not T. longicornis. In conclusion, reproduction of C. typicus was more sensitive to acute elevated seawater CO₂ than that of T. longicornis, but neither species was affected by exposure to CO₂ levels predicted for the year 2100. The duration and seasonal timing of exposures to high pCO₂, however, might have a significant effect on the reproduction success of calanoid copepods.     

Neodymium isotopes in benthic foraminifera: Core-top systematics and a down-core record from the Neogene south Atlantic

Records of the past neodymium (Nd) isotope composition of the deep ocean can resolve ambiguities in the interpretation of other tracers. We present the first Nd isotope data for sedimentary benthic foraminifera. Comparison of the ?_Nd of core-top foraminifera from a depth transect on the Cape Basin side of the Walvis Ridge to published seawater data, and to the modern dissolved SiO₂–?_Nd trend of the deep Atlantic, suggests that benthic foraminifera represent a reliable archive of the deep water Nd isotope composition. Neodymium isotope values of benthic foraminifera from ODP Site 1264A (Angola Basin side of the Walvis Ridge) from the last 8 Ma agree with Fe–Mn oxide coatings from the same samples and are also broadly consistent with existing fish teeth data for the deep South Atlantic, yielding confidence in the preservation of the marine Nd isotope signal in all these archives. The marine origin of the Nd in the coatings is confirmed by their marine Sr isotope values. These important results allow application of the technique to down-core samples.The new ?_Nd datasets, along with ancillary Cd/Ca and Nd/Ca ratios from the same foraminiferal samples, are interpreted in the context of debates on the Neogene history of North Atlantic Deep Water (NADW) export to the South Atlantic. In general, the ?_Nd and δ¹³C records are closely correlated over the past 4.5 Ma. The Nd isotope data suggest strong NADW export from 8 to 5 Ma, consistent with one interpretation of published δ¹³C gradients. Where the ?_Nd record differs from the nutrient-based records, changes in the pre-formed δ¹³C or Cd/Ca of southern-derived deep water might account for the difference. Maximum NADW-export for the entire record is suggested by all proxies at 3.5–4 Ma. Chemical conditions from 3 to 1 Ma are totally different, showing, on average, the lowest NADW export of the record. Modern-day values again imply NADW export that is about as strong as at any stage over the past 8 Ma.     

New insights into the spatial variability of the surface water carbon dioxide in varying sea ice conditions in the Arctic Ocean

In the summer of 2005, continuous surface water measurements of fugacity of CO₂ (fCO₂^sw), salinity and temperature were performed onboard the IB Oden along the Northwest Passage from Cape Farwell (South Greenland) to the Chukchi Sea. The aim was to investigate the importance of sea ice and river runoff on the spatial variability of fCO₂ and the sea–air CO₂ fluxes in the Arctic Ocean. Additional data was obtained from measurements of total alkalinity (A_T) by discrete surface water and water column sampling in the Canadian Arctic Archipelago (CAA), on the Mackenzie shelf, and in the Bering Strait. The linear relationship between A_T and salinity was used to evaluate and calculate the relative fractions of sea ice melt water and river runoff along the cruise track. High-frequency fCO₂^sw data showed rapid changes, due to variable sea ice conditions, freshwater addition, physical upwelling and biological processes. The fCO₂^sw varied between 102 and 678 μatm. Under the sea ice in the CAA and the northern Chukchi Sea, fCO₂^sw were largely CO₂ undersaturated of approximately 100 μatm lower than the atmospheric level. This suggested CO₂ uptake by biological production and limited sea–air CO₂ gas exchange due to the ice cover. In open areas, such as the relatively fresh water of the Mackenzie shelf and the Bering Strait, the fCO₂^sw values were close to the atmospheric CO₂ level. Upwelling of saline and relatively warm water at the Cape Bathurst caused a dramatic fCO₂^sw increase of about 100 μatm relative to the values in the CAA. At the southern part of the Chukchi Peninsula we found the highest fCO₂^sw values and the water was CO₂ supersaturated, likely due to upwelling. In the study area, the calculated sea–air CO₂ flux varied between an oceanic CO₂ sink of 140 mmol m⁻² d⁻¹ and an oceanic source of 18 mmol m⁻² d⁻¹. However, in the CAA and the northern Chukchi Sea, the sea ice cover prevented gas exchange, and the CO₂ fluxes were probably negligible at this time of the year. Assuming that the water was exposed to the atmosphere by total melting and gas exchange would be the only process, the CO₂ undersaturated water in the ice-covered areas will not have the time to reach the atmospheric CO₂ value, before the formation of new sea ice. This study highlights the value of using high-frequency measurements to gain increased insight into the variable and complex conditions, encountered on the shelves in the Arctic Ocean.     

Future seagrass beds: Can increased productivity lead to increased carbon storage?

While carbon capture and storage (CCS) is increasingly recognised as technologically possible, recent evidence from deep-sea CCS activities suggests that leakage from reservoirs may result in highly CO₂ impacted biological communities. In contrast, shallow marine waters have higher primary productivity which may partially mitigate this leakage. We used natural CO₂ seeps in shallow marine waters to assess if increased benthic primary productivity could capture and store CO₂ leakage in areas targeted for CCS. We found that the productivity of seagrass communities (in situ, using natural CO₂ seeps) and two individual species (ex situ, Cymodocea serrulata and Halophila ovalis) increased with CO₂ concentration, but only species with dense belowground biomass increased in abundance (e.g. C. serrulata). Importantly, the ratio of below:above ground biomass of seagrass communities increased fivefold, making seagrass good candidates to partially mitigate CO₂ leakage from sub-seabed reservoirs, since they form carbon sinks that can be buried for millennia.     

Benthic oxygen fluxes and sediment properties on the northeastern New Zealand continental shelf

We examined spatial variations in benthic remineralisation (measured as sediment oxygen consumption (SOC)) and sediment properties on the northeastern New Zealand continental shelf and slope to assess the importance of benthic mineralisation in this ecosystem and to provide data for more complete global carbon budgets. SOC measured in dark incubations conducted in early summer ranged from 128 μmol m⁻² h⁻¹ at the deepest (360 m) to 1222 μmol m⁻² h⁻¹ at the shallowest (4.2 m) site and decreased significantly with water depth (p<0.001, r²=0.78, SOC=1222.8−456.3×log₁₀[water depth], n=14 sites). These rates were in the range found on continental shelves elsewhere (64–1750 μmol m⁻² h⁻¹, n=30 studies) and had a very similar distribution with water depth. SOC was also measured in light incubations at seven sites (4.2–35 m water depth) to examine the effects of microphytobenthos and accounted for 42–106% of rates measured in the dark. Measurements of near-bed light intensities suggested that microphytobenthos production was not solely regulated by light intensity but evidently influenced by other factors. A two-dimensional PCA ordination of surface sediment properties accounted for 83.3% of the total variance in the data and divided the study area into three clusters that corresponded well to its spatial division into the shallow (<30 m) Firth of Thames, the Hauraki Gulf (30–50 m) and the northern shelf-slope region. In the Firth of Thames sediments were very fine-grained with low CaCO₃ and high total organic matter and pigment content, and low C:N ratios. The northern shelf-slope sediments showed the opposite trends to the Firth of Thames and those in the Hauraki Gulf had mostly intermediate values. Dark SOC was significantly correlated with sediment organic matter, carbon, nitrogen, pigments and silt/clay content (p<0.05, r=0.55–0.85) but a multiple linear regression revealed that water depth was the only significant predictor. Calculations suggest that approximately 13%, 10% and 34% of primary production is remineralised in the sediments of the northern shelf-slope region, Hauraki Gulf and Firth of Thames, respectively, indicating a strong benthic–pelagic coupling on the northeastern New Zealand continental shelf that was particularly pronounced in the Firth of Thames due to its shallow depth and significant terrestrial and riverine inputs.     

Stable and radiogenic isotopes as tracers for the origin,mixing and subsurface history of fluids in submarine shallow-water hydrothermal systems

The shallow-water hydrothermal system in Tutum Bay on the west side of Ambitle Island, Papua New Guinea provides us with an exceptional opportunity to study isotope systematics in a near shore setting. Compared to seawater, the hydrothermal fluids in Tutum Bay have lower values for δD, δ¹⁸O, δ¹³C, and ⁸⁷Sr and higher values for ³H, δ³⁴S(SO₄) and δ¹⁸O(SO₄). The δ¹⁸O and δD records for vents 1 and 4 indicate that fluid compositions remained stable over an extended period. Interpretation of isotope data clearly demonstrates the predominantly meteoric origin of Tutum Bay hydrothermal fluids, despite their location in a marine environment. δ¹⁸O and δD values are identical to mean average annual precipitation in eastern Papua New Guinea. The hypothesis that these fluids are a simple product of mixing between seawater and onshore hydrothermal fluids from the Waramung (W-1) and Kapkai (W-2) thermal areas has been rejected, because the observed δ³⁷Cl, ³H, δ³⁴S(SO₄) and δ¹⁸O(SO₄) values cannot be explained by a simple mixing model. The application of δ¹⁸O(SO₄) and δ¹³C thermometers in combination with ³H values corroborates the three-step model of Pichler et al. [Pichler, T., Veizer, J., Hall, G.E.M., 1999. The chemical composition of shallow-water hydrothermal fluids in Tutum Bay, Ambitle Island, Papua New Guinea and their effect on ambient seawater. Marine Chemistry 64 (3) 229–252], where (1) phase separation in the deep reservoir beneath Ambitle Island produces a high temperature vapor that rises upward and subsequently reacts with cooler ground water to form a low pH, CO₂-rich water of approximately 150–160 °C, (2) caused by the steep topography, this CO₂-rich fluid moves laterally towards the margin of the hydrothermal system where it mixes with the marginal upflow of the deep reservoir fluid. This produces a dilute chloride water of approximately 165 °C, and (3) possibly the entrainment of minor amounts of ground or seawater during its final ascent.     

Inorganic carbon dynamics during northern California coastal upwelling

Coastal upwelling events in the California Current System can transport subsurface waters with high levels of carbon dioxide (CO₂) to the sea surface near shore. As these waters age and are advected offshore, CO₂ levels decrease dramatically, falling well below the atmospheric concentration beyond the continental shelf break. In May 2007 we observed an upwelling event off the coast of northern California. During the upwelling event subsurface respiration along the upwelling path added ∼35 μmol kg⁻¹ of dissolved inorganic carbon (DIC) to the water as it transited toward shore causing the waters to become undersaturated with respect to Aragonite. Within the mixed layer, pCO₂ levels were reduced by the biological uptake of DIC (up to 70%), gas exchange (up to 44%), and the addition of total alkalinity through CaCO₃ dissolution in the undersaturated waters (up to 23%). The percentage contribution of each of these processes was dependent on distance from shore. At the time of measurement, a phytoplankton bloom was just beginning to develop over the continental shelf. A box model was used to project the evolution of the water chemistry as the bloom developed. The biological utilization of available nitrate resulted in a DIC decrease of ∼200 μmol kg⁻¹, sea surface pCO₂ near ∼200 ppm, and an aragonite saturation state of ∼3. These results suggest that respiration processes along the upwelling path generally increase the acidification of the waters that are being upwelled, but once the waters reach the surface biological productivity and gas exchange reduce that acidification over time.     

Fumarolic emissions from Mount St. Augustine,Alaska: 1979–1984 degassing trends,volatile sources and their possible role in eruptive style

Gas samples were collected from high-temperature, rooted summit vents at Mount St. Augustine in 1979, 1982, and 1984. All of the gas samples exhibit various degrees of disequilibrium. Thermodynamic restoration of the analyzed gases permits partial or complete removal of these disequilibrium effects and allows inference of equilibrium gas compositions. Long-term (1979–1984) degassing trends within resampled or adjacent vents are characterized by increases (from 97.4 to 99.8 mole%) in the H₂O fraction and major decreases in the residual gases. Over this same period total gas HCl contents decreased by a factor of 3 to 10 while dry gas (H₂O-free recalculated) HCl contents increased by a factor of 1.6 to 3. Dry gas mole proportions at these sites changed from being CO₂-dominated (46% CO₂, 24% H₂ in 1979) to H₂-dominated (49% H₂, 22% CO₂ in 1984). The overall trends in gas chemistry and the stable isotope patterns in gases and condensates from the summit fumaroles can be explained by progressive magmatic outgassing coupled with increasing proportions of seawater in the fumarole emissions.Studies of the gaseous emissions following the 1976 and 1986 Mount St. Augustine eruptions confirmed the Cl- and S-rich nature of the Mount St. Augustine emanations. Seawater, possibly derived from magmatic assimilation or dehydration of near-surface seawater-bearing sediments, could supply a portion of the outgassed Cl and S. Continued seawater influx through subvolcanic fractures or permeable sediments would recharge the seawater-depleted zone and provide a near-surface Cl and S source for the next eruptive cycle,Various lines of evidence support a phreatomagmatic component in the 1976 and 1986 Mount St. Augustine eruptions. We suggest that seawater may interact with magma or volcanic gases during the early explosive phase of Mount St. Augustine eruptions and that it continues to influence high-temperature fumarole emissions as the volcanic system cools.     

Glacial atmospheric CO2 decline in association with decrease of marine sedimentary phosphorus

The environmental and biogeochemical information extracted from the sediments collected from the northern shelf of the South China Sea shows that terrigenous inputs of phosphorus into the sea remained relatively constant, and the variation of phosphorus contents at different depths was caused by climatic and environmental changes. The findings also suggest that the vertical variation of phosphorus content was opposite to those of calcium carbonate and cadmium, and the functional correlation between CO₂ and PO ₄ ³⁻ in seawater was given by calculating the chemical equilibrium, indicating that the accumulation of marine sedimentary phosphorus may have something to do with the variation of atmospheric CO₂. The decreased phosphorus accumulation as well as the correspondingly-increased calcium carbonate content might be one of key factors causing glacial atmospheric CO₂ decline.     

Ostreopsis cf. ovata bloom in the northern Adriatic Sea during summer 2009: ecology, molecular characterization and toxin profile

Intense blooms of the benthic dinoflagellate Ostreopsis cf. ovata have occurred in the northern Adriatic Sea since 2006. These blooms are associated with noxious effects on human health and with the mortality of benthic organisms because of the production of palytoxin-like compounds. The O. cf. ovata bloom and its relationships with nutrient concentrations at two stations on the Conero Riviera (northern Adriatic Sea) were investigated in the summer of 2009. O. cf. ovata developed from August to November, with the highest abundances in September (1.3 × 10⁶ cells g⁻¹ fw corresponding to 63.8 × 10³ cells cm⁻²). The presence of the single O. cf. ovata genotype was confirmed by a PCR assay. Bloom developed when the seawater temperature was decreasing. Nutrient concentrations did not seem to affect bloom dynamics. Toxin analysis performed by high resolution liquid chromatography-mass spectrometry revealed a high total toxin content (up to 75 pg cell⁻¹), including putative palytoxin and all the ovatoxins known so far.     

The effect of thermal pollution on benthic foraminiferal assemblages in the Mediterranean shoreface adjacent to Hadera power plant (Israel)

The thermal pollution patch of Hadera power plant was used as a natural laboratory to evaluate the potential long-term effects of rise in Eastern Mediterranean SST on living benthic foraminifera. Their sensitivity to environmental changes makes foraminifera ideal for this study. Ten monthly sampling campaigns were performed in four stations located along a temperature gradient up to 10 °C from the discharge site of heated seawater to a control station. The SST along this transect varied between 25/18 °C in winter and 36/31 °C in summer. A significant negative correlation was found between SST in all stations and benthic foraminiferal abundance, species richness and diversity. The total foraminiferal abundance and species richness was particularly low at the thermally polluted stations especially during summer when SST exceeded 30 °C, but also throughout the entire year. This indicates that thermal pollution has a detrimental effect on benthic foraminifera, irrelevant to the natural seasonal changes in SST.     

Modern and Pleistocene boron isotope composition of the benthic foraminifer Cibicidoides wuellerstorfi

Here we present the first species-specific study of boron isotopes in the epibenthic foraminifer species Cibicidoides wuellerstorfi. Coretop samples from a water depth profile from 1000 to 4500 m on the northern flank of the Walvis Ridge are 4.4‰ lower than the values expected, based on calculations of the δ¹¹B_borate of ambient seawater. Similar values for this foraminifer species are presented from ODP site 668B at the Sierra Leone Rise, in the equatorial Atlantic. The consistency between data of the same species suggests the offsets are primary, rather than diagenetic. Glacial C. wuellerstorfi from ODP 668B and Walvis Ridge have boron isotope compositions only slightly different to interglacial samples, that is no larger than + 0.10 pH units, or + 23 µmol kg^− 1 in [CO₃²⁻] above the reconstructed glacial lysocline, and − 0.07 pH units, or − 14 µmol kg^− 1 in [CO₃²⁻] below. We use these results to suggest that glacial deep water pH in the Atlantic was similar to interglacial pH. The new data resolve the inconsistency between the previously reported high bottom water pH and the lack of significant carbonate preservation of the glacial deep ocean.